Lubricating oil additive composition and method of making the same

ABSTRACT

An oil-soluble lubricating oil additive composition prepared by the process which comprises reacting a copolymer, with at least one polyether aromatic compound, and with at least one polyether aliphatic compound.

FIELD OF THE INVENTION

The present invention is directed to an improved dispersant additivecomposition that is used in engine oils; and it is also directed to theprocess of making the same.

BACKGROUND OF THE INVENTION

It is known to employ nitrogen containing dispersants and/or detergentsin the formulation of lubricating oil compositions. Many of the knowndispersant/detergent compounds are based on the reaction of analkenylsuccinic acid or anhydride with an amine or polyamine to producean alkenylsuccinimide or an alkenyl succinamic acid as determined byselected conditions of reaction. One problem facing the lubricantmanufacturer is dispersancy of particulate matter in internal combustionengines. Failure to have adequate particulate matter dispersancy mayresult in filter plugging, sludge accumulation, and oil thickening.

DESCRIPTION OF THE RELATED ART

Liu et al., U.S. Pat. No. 6,117,825, discloses a lubricating oilcomposition that comprises a major amount of an oil of lubricatingviscosity; and a minor amount of a synergistic combination of anantioxidant-dispersant additive and a dispersant additive, saidcombination comprising: (i) a polyisobutylene succinimide (PIBSAD) and(ii) an ethylene-propylene succinimide (LEPSAD).

Nalesnik, U.S. Pat. No. 5,138,688, discloses an additive compositioncomprising an oxidized ethylene copolymer or terpolymer of a C₃-C₁₀alpha-monoolefin and, optionally, a non-conjugated diene or triene whichhas been reacted with a formaldehyde compound and with an amino-aromaticpolyamine compound.

Günther et al., U.S. Pat. No. 6,512,055, discloses a copolymer obtainedby free radical copolymerization of at least one monoethylenicallyunsaturated C₄-C₆ dicarboxylic acid or anhydride thereof, an oligomer,and one monoethylenically unsaturated compound.

Günther et al., U.S. Pat. No. 6,284,716, discloses a lubricating oilcomposition comprising a lubricant oil and a copolymer obtained by, freeradical, copolymerization of at least one monoethylenically unsaturatedC₄-C₆ dicarboxylic acid or anhydride thereof, an oligomer, and onemonoethylenically unsaturated compound, wherein the copolymer is furtherreacted with an amine.

Harrison et al., U.S. Pat. No. 5,792,729, discloses a dispersantterpolymer and polysuccinimide compositions derived from theterpolymers. The terpolymer is obtained by free radical copolymerizationof an unsaturated acidic reagent, a 1-olefin, and a 1,1-disubstitutedolefin in the presence of a free radical initiator.

Barr et al., U.S. Pat. No. 5,670,462, discloses a lubricating oiladditive composition that is the reaction product of (i) a copolymerizedolefin and unsaturated carboxylic acylating agent monomer with a freeradical initiator and (ii) a succinimide prepared from an acyclichydrocarbyl substituted succinic acylating agent and a polyamine whereinthe hydrocarbyl substituted succinic acylating agent is prepared byreacting a polyolefin and an acylating agent under conditions such thatat least 75 mole % of the starting polyolefin is converted to thehydrocarbyl-substituted succinic acylating agent.

Harrison et al., U.S. Pat. No. 6,451,920, discloses copolymerizing apolyalkene and an unsaturated acidic reagent, followed by reacting anyunreacted polyalkene with the unsaturated acidic reagent at elevatedtemperatures in the presence of a strong acid.

Chung et al., U.S. Pat. Nos. 5,427,702 and 5,744,429, disclose a mixtureof derivatized ethylene-alpha olefin copolymers, wherein functionalgroups are grafted onto the copolymer. The functionialized copolymer ismixed with at least one of an amine, alcohol, including polyol, aminoalcohol etc. to form multi-functional viscosity index improver additivecomponents.

Harrison et al., U.S. Pat. No. 5,112,507, discloses novel copolymers ofunsaturated acidic reactants and high molecular weight olefins whereinat least 20% of the total high molecular weight olefin comprises thealkylvinylidene isomer which copolymers are useful as dispersants inlubricating oils and fuels and also may be used to preparepolysuccinimides and other post-treated additives useful in lubricatingoils, and fuels.

SUMMARY OF THE INVENTION

In its broadest embodiment, the present invention is directed to anoil-soluble lubricating oil additive composition prepared by the processwhich comprises reacting

-   (A) at least one of the following copolymers:    -   (i) a copolymer obtained by free radical copolymerization of        components comprising:        -   (a) at least one monoethylenically unsaturated C₃-C₂₈            monocarboxylic acid of ester thereof, or C₄-C₂₈ dicarboxylic            acid, anhydride or ester thereof;        -   (b) at least one 1-olefin comprising about 2 to 40 carbon            atoms or at least one polyolefin comprising about 4 to 360            carbon atoms and having a terminal copolymerizable group in            the form of a vinyl, vinylidene or alkyl vinylidene group or            mixtures thereof; and        -   (c) at least one monoolefin compound which is            copolymerizable with the monomers of (a) and (b) and is            selected from the group consisting of:            -   (1) an alkyl vinyl ether and an allyl alkyl ether where                the alkyl group is hydroxyl, amino, dialkylamino or                alkoxy substituted or is unsubstituted, and containing                from about 1 to about 40 carbon atoms;            -   (2) an alkyl amine and an N-alkylamide of a                monoethylenically unsaturated mono- or dicarboxylic acid                of from about 3 to about 10 carbon atoms where the alkyl                substituent contains from about 1 to about 40 carbon                atoms;            -   (3) an N-vinylcarboxamide of carboxylic acids of from                about 1 to about 8 carbon atoms;            -   (4) an N-vinyl substituted nitrogen-containing                heterocyclic compound; and            -   (5) at least one 1-olefin comprising from about 2 to                about 40 carbon atoms or at least one polyolefin                comprising from about 4 to about 360 carbon atoms and                having a terminal copolymerizable group in the form of a                vinyl, vinylidene or alkyl vinylidene group or mixtures                thereof, provided that the olefin employed is not the                same as the olefin employed in (i)(b);    -   (ii) a copolymer obtained by reacting compound (i)(a) and        compound (i)(b) in the presence of a free radical initiator;    -   (iii) a copolymer obtained by (a) reacting compound (i)(a) with        compound (i)(b) or (i)(c) in a non-free radical catalyzed        reaction in the presence of copolymer (i) or copolymer (ii) or        both; or by (b) contacting copolymer (i) or copolymer (ii) or        both with the non-free radical catalyzed reaction product of        compound (i)(a) and compound (i)(b) or (i)(c), wherein the        copolymer of (i), (ii) or (iii); with-   (B) at least one polyether aromatic compound capable of being    reacted with at least two monocarboxylic acids or esters thereof, or    with at least two, dicarboxylic acids, anhydrides or esters thereof,    or mixtures thereof; and-   (C) at least one polyether aliphatic amine compound capable of being    reacted with at least two monocarboxylic acids or esters thereof; or    at least two dicarboxylic acids, anhydrides, or esters thereof; or    mixtures thereof.

The present invention is also directed to a lubricating oil compositioncomprising a major amount of an oil of lubricating viscosity and a minoramount of the lubricating oil additive composition prepared by theprocess which comprises reacting

-   (A) at least one of the following copolymers:    -   (i) a copolymer obtained by free radical copolymerization of        components comprising:        -   (a) at least one monoethylenically unsaturated C₃-C₂₈            monocarboxylic acid or ester thereof, or C₄-C₂₈ dicarboxylic            acid, anhydride or ester thereof;        -   (b) at least one 1-olefin comprising about 2 to about 40            carbon atoms or at least one polyolefin comprising from            about 4 to about 360 carbon atoms and having a terminal            copolymerizable group in the form of a vinyl, vinylidene or            alkyl vinylidene group or mixtures thereof; and        -   (c) at least one monoolefin compound which is            copolymerizable with the monomers of (a) and (b) and is            selected from the group consisting of:            -   (1) an alkyl vinyl ether and an allyl alkyl ether where                the alkyl group is hydroxyl, amino, dialkylamino or                alkoxy substituted or is unsubstituted, and containing                from about 1 to about 40 carbon atoms;            -   (2) an alkyl amine and an N-alkylamide of a                monoethylenically unsaturated mono- or dicarboxylic acid                of from about 3 to about 10 carbon atoms where the alkyl                substituent contains from about 1 to about 40 carbon                atoms;            -   (3) an N-vinylcarboxamide of carboxylic acids of from                about 1 to about 8 carbon atoms;            -   (4) an N-vinyl substituted nitrogen-containing                heterocyclic compound; and            -   (5) at least one 1-olefin comprising from about 2 to                about 40 carbon atoms or at least one polyolefin                comprising from about 4 to about 360 carbon atoms and                having a terminal copolymerizable group in the form of a                vinyl, vinylidene or alkyl vinylidene group or mixtures                thereof, provided that the olefin employed is not the                same as the olefin employed in (i)(b);    -   (ii) a copolymer obtained by reacting compound (i)(a) and        compound (i)(b) in the presence of a free radical initiator;    -   (iii) a copolymer obtained by (a) reacting compound (i)(a) with        compound (i)(b) or (i)(c) in a non-free radical catalyzed        reaction in the presence of copolymer (i) or copolymer (ii) or        both; or by (b) contacting copolymer (i) or copolymer (ii) or        both with the non-free radical catalyzed reaction product of        compound (i)(a) and compound (i)(b) or (i)(c); with-   (B) at least one polyether aromatic compound capable of being    reacted with at least two monocarboxylic acids or esters thereof, or    with at least two dicarboxylic acids, anhydrides of esters thereof,    or mixtures thereof; and-   (C) at least one polyether aliphatic amine compound capable of being    reacted with at least two monocarboxylic acids or esters thereof; or    at least two dicarboxylic acids, anhydrides, or esters thereof; or    mixtures thereof.-   The present invention is also directed to a method of making a    lubricating oil additive composition which comprises reacting-   (A) at least one of the following copolymers:    -   (i) a copolymer obtained by free radical copolymerization of        components comprising:        -   (a) at least one monoethylenically unsaturated C₃-C₂₈            monocarboxylic acid or ester thereof, or C₄-C₂₈ dicarboxylic            acid, anhydride or ester thereof;        -   (b) at least one 1-olefin comprising from about 2 to about            40 carbon atoms or at least one polyolefin comprising from            about 4 to about 360 carbon atoms and having a terminal            copolymerizable group in the form of a vinyl, vinylidene or            alkyl vinylidene group or mixtures thereof; and        -   (c) at least one monoolefin compound which is            copolymerizable with the monomers of (a) and (b) and is            selected from the group consisting of:            -   (1) an alkyl vinyl ether and an ally alkyl ether where                the alkyl group is hydroxyl, amino, dialkylamino or                alkoxy substituted or is unsubstituted and containing                from about 1 to about 40 carbon atoms;            -   (2) an alkyl amine and an N-alkylamide of a                monoethylenically unsaturated mono- or dicarboxylic acid                of from about 3 to about 10 carbon atoms where the alkyl                substituent contains from about 1 to about 40 carbon                atoms;            -   (3) an N-vinylcarboxamide of carboxylic acids of from                about 1 to about 8 carbon atoms;            -   (4) an N-vinyl substituted nitrogen-containing                heterocyclic compound; and            -   (5) at least one 1-olefin comprising from about 2 to                about 40 carbon atoms or at least one polyolefin                comprising from about 4 to about 360 carbon atoms and                having a terminal copolymerizable group in the form of a                vinyl, vinylidene or alkyl vinylidene group or mixtures                thereof, provided that the olefin employed is not the                same as the olefin employed in (i)(b);    -   (ii) a copolymer obtained by reacting compound (i)(a) and        compound (i)(b) in the presence of a free radical initiator;    -   (iii) a copolymer obtained by (a) reacting compound (i)(a) with        compound (i)(b) or (i)(c) in a non-free radical catalyzed        reaction in the presence of copolymer (i) or copolymer (ii) or        both; or by (b) contacting copolymer (i) or copolymer (ii) or        both with the non-free radical catalyzed reaction product of        compound (i)(a) and compound (i)(b) or (i)(c); with-   (B) at least one polyether aromatic compound capable of being    reacted with at least two monocarboxylic acids or esters thereof, or    with at least two dicarboxylic acids, anhydrides or esters thereof,    or mixtures thereof; and-   (C) at least one polyether aliphatic amine compound capable of being    reacted with at least two monocarboxylic acids or esters thereof; or    at least two dicarboxylic acids, anhydrides, or esters thereof; or    mixtures thereof.

Accordingly, the present invention relates to multi-functionallubricating oil additives which are useful as dispersants in an internalcombustion engine.

DETAILED DESCRIPTION OF THE INVENTION

While the invention is susceptible to various modifications andalternative forms, specific embodiments thereof and are, hereindescribed in detail. It should be understood, however, that thedescription herein of specific embodiments is not intended to limit theinvention to the particular forms disclosed, but on the contrary, theintention is to cover all modifications, equivalents, and alternativesfalling within the spirit and scope of the invention as defined by theappended claims.

DEFINITIONS

The following terms used with the description are defined as such:

The term “PIB” is an abbreviation for polyisobutene.

The term “PIBSA” is an abbreviation for polyisobutenyl or polyisobutylsuccinic anhydride.

The term “polyPIBSA” refers to a class of copolymers employed within thescope of the present invention which are copolymers of polyisobutene anda monoethylenically unsaturated C₃-C₂₈ monocarboxylic acid or esterthereof, or a C₄-C₂₈ dicarboxylic acid, anhydride or ester thereof whichhave carboxyl groups, preferably succinic groups, and polyisobutylgroups. The preferred polyPIBSA is a copolymer of polyisobutene andmaleic anhydride having the general formula:

wherein n is one or greater; R₁R₂, R₃ and R₄ are selected from hydrogen,methyl and polyisobutyl having at least about 8 carbon atoms, preferablyat least about 30 carbon atoms and more preferably at least about 50carbon atoms wherein either R₁ and R₂ are hydrogen and one of R₃ and R₄is methyl and the other is polyisobutyl, or R₃ and R₄ are hydrogen andone of R₁ and R₂ is methyl and the other is polyisobutyl. The polyPIBSAcopolymer may be alternating, block, or random.

The term “succinic group” refers to a group having the formula:

wherein W and Z are independently selected from the group consisting of—OH, —Cl, —O-alkyl or taken together are —O— to form a succinicanhydride group. The term “—O-alkyl” is meant to include alkoxy of fromabout 1 to about 40 carbon atoms, preferably from about 1 to about 8carbon atoms.

The term “degree of polymerization” refers to the average number ofrepeating structural units in the polymer chain.

The term “terpolymer” refers to a polymer derived from the free radicalcopolymerization of at least 3 monomers.

The term “1-olefin” refers to a monounsaturated olefin that has thedouble bond in the 1-position. They can also be called alpha-olefins,and have, the following structure:CH₂═CHR

where R is the rest of the olefin molecule.

The term “1,1-disubstituted olefin” refers to a disubstituted olefin,also called a vinylidene olefin, that has the following structure:CH₂═CR₅R₆

wherein R₅ and R₆ are the same or different, and constitute the rest ofthe olefin, molecule. Preferably, either R₅ or R₆ is a methyl group, andthe other is not.

The term “succinimide” is understood in the art to include many of theamide, imide, etc. species which are also formed by the reaction of asuccinic anhydride with an amine. The predominant product, however, issuccinimide and this term has been generally accepted as meaning theproduct of a reaction of an alkenyl- or alkyl-substituted succinic acidor anhydride with an amine. Alkenyl or alkyl succinimides are disclosedin numerous references and are well known in the art. Certainfundamental types of succinimides and related materials encompassed bythe term of art “succinimide” are taught in U.S. Pat. Nos. 2,992,708;3,018,291; 3,024,237; 3,100,673; 3,219,666; 3,172,892; and 3,272,746,the disclosures of which are hereby incorporated by reference.

The term “polysuccinimide” refers to the reaction product of a succinicgroup-containing copolymer with an amine.

The term “alkenyl or alkylsuccinic acid derivative” refers to astructure having the formula:

wherein R₇ is selected from hydrogen, methyl and polyisobutyl having atleast about 8 carbon atoms, preferably at least about 30 carbon atomsand more preferably at least about 50 carbon atoms; wherein L and M areindependently selected from the group consisting of —OH, —Cl, —O-alkylof taken together are —O— to form an alkenyl or alkylsuccinic anhydridegroup.

The term “alkylvinylidene” or “alkylvinylidene isomer” refers to anolefin having the following vinylindene structure:

wherein R₈ is alkyl or substituted alkyl. R₈ generally has at leastabout 5 carbon atoms, preferably about 30 carbon atoms, and morepreferably at least about 50 carbon atoms and R₉ is lower alkyl of fromabout 1 to about 6 carbon atoms.

The term “soluble in lubricating oil” refers to the ability of amaterial to dissolve in aliphatic and aromatic hydrocarbons such aslubricating oils or fuels in essentially all proportions.

The term “high molecular weight olefins” refers to olefins (includingpolymerized olefins having a residual unsaturation) of sufficientmolecular weight and chain length to lend solubility in lubricating oilto their reaction products. Typically olefins having about 30 carbons ormore suffice.

The term “high molecular weight polyalkyl” refers to polyalkyl groups ofsufficient molecular weight such that the products prepared having suchsufficient molecular weight are soluble in lubricating oil. Typicallythese high molecular weight polyalkyl groups have at least about 30carbon atoms, preferably at least about 50 carbon atoms. These highmolecular weight polyalkyl groups may be derived from high molecularweight polyolefins.

The term “amino” refers to —NR₁₀R₁₁ wherein R₁₀ and R₁₁ areindependently hydrogen or a hydrocarbyl group.

The term “alkyl” refers to both straight- and branched-chain alkylgroups.

The term “lower alkyl” refers to alkyl groups having from about 1 toabout 6 carbon atoms and includes primary, secondary and tertiary alkylgroups. Typical lower alkyl groups include, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, sec-butyl, t-butyl, n-pentyl, iso-pentyl,n-hexyl and the like.

The term “polyalkyl” refers to an alkyl group that is generally derivedfrom polyolefins which are polymers of copolymers of mono-olefins,particularly 1-mono-olefins, such as ethylene, propylene, butylene, andthe like. Preferably, the mono-olefin employed will have from about 2 toabout 24 carbon atoms and more preferably, from about 3 to about 12carbon atoms. More preferred mono-olefins include propylene, butylene,particularly isobutylene, 1-octene and 1-decene. Preferred, polyolefinsprepared from such mono-olefins include polypropylene, polybutene,especially polyisobutene.

The Lubricating Oil Additive Composition

One embodiment of the present invention is an oil-soluble lubricatingoil additive composition prepared by the process which comprisesreacting

-   (A) at least one of the following copolymers:    -   (i) a copolymer obtained by free radical copolymerization of        components comprising:        -   (a) at least one monoethylenically unsaturated C₃-C₂₈            monocarboxylic acid or ester thereof, of C₄-C₂₈ dicarboxylic            acid, anhydride or ester thereof;        -   (b) at least one 1-olefin comprising about 2 to 40 carbon            atoms of at least one polyolefin comprising about 4 to 360            carbon atoms and having a terminal copolymerizable group in            the form of a vinyl, vinylidene or alkyl vinylidene group or            mixtures thereof; and        -   (c) at least one monoolefin compound which is            copolymerizable with the monomers of (a) and (b) and is            selected from the group consisting of:            -   (1) an alkyl vinyl ether and an ally alkyl ether, where                the alkyl group is hydroxyl, amino, dialkylamino or                alkoxy substituted or is unsubstituted, and containing 1                to 40 carbon atoms;            -   (2) an alkyl amine and an N-alkylamide of a                monoethylenically unsaturated mono- or dicarboxylic acid                of 3 to 10 carbon atoms where the alkyl substituent                contains 1 to 40 carbon atoms;            -   (3) an N-vinylcarboxamide of carboxylic acids of 1 to 8                carbon atoms;            -   (4) an N-vinyl substituted nitrogen-containing                heterocyclic compound; and            -   (5) at least one 1-olefin comprising about 2 to 40                carbon atoms or at least one polyolefin comprising about                4 to about 360 carbon atoms and having a terminal                copolymerizable group in the form of a vinyl, vinylidene                or alkyl vinylidene group or mixtures thereof, provided                that the olefin employed is not the same as the olefin                employed in (i)(b);    -   (ii) a copolymer obtained by reacting compound (i)(a) and        compound (i)(b) in the presence of a free radical initiator;    -   (iii) a copolymer obtained by (a) reacting compound (i)(a) with        compound (i)(b) or (i)(c) in a non-free radical catalyzed        reaction in the presence of copolymer (i) or copolymer (ii) or        both; or by (b) contacting copolymer (i) or copolymer (ii) or        both with the non-free radical catalyzed reaction product of        compound (i)(a) and compound (i)(b) or (i)(c); with-   (B) at least one polyether aromatic compound capable of being    reacted with at least two monocarboxylic acids or esters thereof, or    with at least two dicarboxylic acids, anhydrides or esters thereof,    or mixtures thereof; and-   (C) at least one polyether aliphatic amine compound capable of being    reacted with at least two monocarboxylic acids or esters thereof; or    at least two dicarboxylic acids, anhydrides, or esters thereof; or    mixtures thereof.

Copolymer (i)

(a) The Monoethylenically Unsaturated Monocarboxylic-Acid or EsterThereof or Dicarboxylic Acid, Anhydride or Ester Thereof

In the present invention, at least one monoethylenically unsaturatedC₃-C₂₈ monocarboxylic acid or ester thereof, of C₄-C₂₈ dicarboxylicacid, anhydride or ester thereof is used to prepare the copolymers ofcopolymer (i). Preferably the at least one monoethylenically unsaturatedC₃-C₂₈ monocarboxylic acid or ester thereof, or C₄-C₂₈ dicarboxylicacid, anhydride or ester thereof is a dicarboxylic acid, anhydride orester thereof.

The general formula of the preferred dicarboxylic acid, anhydride orester thereof is as follows:

wherein X and X′ are the same or different, provided that at least oneof X and X′ is a group that is capable of reacting to esterify alcohols,form amides or, amine salts with ammonia or amines, form metal saltswith reactive metals or basically reacting metal compounds and otherwisefunction as acylating agent's. Typically, X and/dr X′ is —OH,—O-hydrocarbyl, OM+ where M+ represents one equivalent of a metal,ammonium or amine cation, —NH₂, —Cl, —Br, and taken together X and X′can be —O— so as to form an anhydride. Preferably X and X′ are such thatboth carboxylic functions can enter into acylation reactions. Maleicanhydride is a preferred reactant. Other suitable reactants includeelectron-deficient olefins such as monophenyl maleic anhydride;monomethyl, dimethyl, monochloro, monobromo, monofluoro, dichloro anddifluoro maleic anhydride; N-phenylmaleimide and other substitutedmaleimides, isomaleimides; fumaric acid, maleic acid, alkyl hydrogenmaleates and fumarates, dialkyl fumarates and maleates, fumaronilicacids and maleanic acids; and maleonitrile and fumaronitrile.

Suitable monomers for (a) are monoethylenically unsaturated dicarboxylicacids or anhydrides of from about 4 to 28 carbon atoms selected from thegroup consisting of maleic acid, fumaric acid, itaconic acid, mesaconicacid, methylenemalonic acid, citraconic acid, maleic anhydride, itaconicanhydride, citraconic anhydride and methylenemalonic anhydride andmixtures of these with one another among which maleic anhydride ispreferred.

Other suitable monomers are monoethylenically unsaturatedC₃-C₂₈-monocarboxylic acids selected from the group consisting ofacrylic acid, methacrylic acid, dimethacrylic acid, ethylacrylic acid,carbonic acid, allylacetic acid and vinylacetic acid, among whichacrylic and methacrylic acid are preferred.

Another group of suitable monomers is C₁-C₄₀ alkyl esters ofmonoethylenecially unsaturated C₃-C₁₀ mono- or C₄-C₁₀ dicarboxylic acidssuch as ethyl acrylate, butyl acrylate, 2-ethyl acrylate, decylacrylate, docedyl acrylate, loctadecyl acrylate and the esters ofindustrial alcohol mixtures of from about 14 to 28 carbon atoms, ethylmethacrylate, 2-ethylhexyl methacrylate, decyl methacrylate, octadecylmethacrylate, monobutyl maleate, dibutyl maleate, monodecyl maleate,didodecyl maleate, monooctadecyl maleate, and dioctadecyl maleate.

(b) The 1-Olefin or Polyolefin

In the present invention at least one 1-olefin comprising about 2 to 40carbon atoms or at least one polyolefin comprising about 4 to 360 carbonatoms and having a terminal copolymerizable group in the form of vinyl,vinylidene or alkyl vinylidene group is employed.

Suitable 1-olefins for preparing copolymer (i) comprise from about 2 toabout 40 carbon atoms, preferably from about 6 to about 30 carbon atoms,such as decene, dodecene, octadecene and mixtures of C₂₀-C₂₄-1-olefinsand C₂₄-C₂₈-1-olefins, more, preferably from about 10 to about 20 carbonatoms. Preferably 1-olefins, which are also known as alpha olefins, withnumber average molecular weights in the range 100-4,500 or more arepreferred, with molecular weights in the range of 200-2,000 being morepreferred. For example alpha olefins obtained from the thermal crackingof paraffin wax. Generally, these olefins range from about 5 to about 20carbon atoms in length. Another source of alpha olefins is the ethylenegrowth process which gives even number carbon olefins. Another source ofolefins is by the dimerization of alpha olefins over an appropriatecatalyst such as the well known Ziegler catalyst. Internal olefins areeasily obtained by the isomerization of alpha olefins over a suitablecatalyst such as silica. Preferably, 1-olefins from C₆-C₃₀ are usedbecause these materials are commercially readily available, and becausethey offer a desirable balance of the length of the molecular tail, andthe solubility of the terpolymer in nonpolar solvents. Mixtures ofolefins may also be employed.

Suitable polyolefins for preparing copolymer (i) are polyolefinscomprising about 4 to about 360 carbon atoms. These polymers have anumber average molecular weight (M_(n)) of from about 56 to about 5000g/mol. Examples of these are oligomers of ethylene, of butene, includingisobutene, and of branched isomers of pentene, hexene, octene and ofdecene, the copolymerizable terminal group, of the oligomer beingpresent in the form of a vinyl, vinylidene or alkylvinylidene group,oligopropenes and oligopropene mixtures of from about 9 to about 200carbon atoms and in particular oligoisobutenes, as obtainable, forexample, according to DE-A 27 02 604, corresponding U.S. Pat. No.4,152,499, are preferred. Mixtures of the stated oligomers are alsosuitable, for example mixtures of ethylene and other alpha olefins.Other suitable polyolefins are described in U.S. Pat. No. 6,030,930which is herein incorporated by reference. The molecular weights of theoligomers may be determined in a conventional manner by gel permeationchromatography.

The copolymerizable polyolefin that is reacted with the unsaturatedmono- or di-carboxylic reactant are polymers comprising a major amountof C₂-C₈ mono-olefin, e.g., ethylene, propylene, butylene, isobutyleneand pentene. These polymers can be homopolymers such as polyisobutyleneas well as copolymers of 2 or more such olefins such as copolymers of:ethylene and propylene, butylene, and isobutylene, etc.

The polyolefin polymer usually contains from about 4 to about 360 carbonatoms, although preferably 8 to 200 carbon atoms; and more preferablyfrom about 12 to about 175 carbon atoms.

Since the high molecular weight olefins used to prepare the copolymersof the present invention are generally mixtures, of individual moleculesof different molecular weights, individual copolymer molecules resultingwill generally contain a mixture of high molecular weight polyalkylgroups of varying molecular weight. Also, mixtures of copolymermolecules having different degrees of polymerization will be produced.

The copolymers of the present invention have an average degree ofpolymerization of 1 or greater, preferably from about 1.1 to about 20,and more preferably from about 1.5 to about 10.

(c) The Mono-Olefin Compound

The present invention employs at least one monoolefin compound which iscopolymerizable with the monomers of (a) and (b) and is selected fromthe group consisting of:

-   (1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl    group is hydroxyl, amino, dialkylamino or alkoxy substituted or is    unsubstituted, and containing from about 1 to about 40 carbon atoms;

Suitable monomers include the following: vinyl and allyl alkyl etherswhere the alkyl radical is of about 1 to about 40 carbon atoms are alsosuitable, and the alkyl radical may carry further substituents, such ashydroxyl, amino, dialkyamino or alkoxy. Examples are methyl vinyl ether,ethyl vinyl ether, propyl vinyl ether, isobutyl vinyl ether,2-ethylhexyl vinyl ether, decylvinyl ether, dodecyl vinyl ether,octadecyl vinyl ether, 2-(diethylyamino)ethyl vinyl ether,2-(di-n-butylamino)ethyl vinyl ether, and the corresponding allylethers.

-   (2) an alkyl amine and an N-alkylamide of a monoethylenically    unsaturated mono- or dicarboxylic acid of from about 3 to about 10    carbon atoms where the alkyl substituent contains from about 1 to    about 40 carbon atoms;

Another group of monomers comprises C₁-C₄₀ alkyl amines andC₁-C₄₀—N-alkylamides of monoethylenically unsaturated C₃-C₁₀-mono- ordicarboxylic acids, such as dimethylaminoethyl acrylate,diethylaminoethyl acrylate, dibutylaminoethyl methacrylate, acrylamidemethacrylamide, N-tert-butylacrylamide, N-octylacrylamide,N,N′-dibutylacrylamide, N-dodecylmethacrylamide andN-octadecylmethacrylamide.

-   (3) an N-vinylcarboxamide of carboxylic; acids of from about 1 to    about 8 carbon atoms;    -   Another group of monomers includes the following:        N-vinylcarboxamides of carboxylic acids of from about 1 to about        8 carbon atoms, such as N-vinylformamide,        N-vinyl-N-methylformamide, N-vinylacetamide,        N-vinyl-N-methylacetramide, N-vinyl-N-ethylacetamide,        N-vinyl-N-methylpropionamide and N-vinylpropionamide.-   (4) an N-vinyl substituted nitrogen-containing heterocyclic    compound; Another group of monomers includes the following: N-vinyl    compounds of nitrogen-containing heterocyles, such as    N-vinylimidazole, N-vinylmethylimidazole, N-vinylpyrrolidone and    N-vinylcaprolactam.-   (5) at least one 1-olefin comprising about 2 to 40 carbon atoms or    at least one polyolefin comprising from about 4 to about 360 carbon    atoms and having a terminal copolymerizable group in the form of a    vinyl, vinylidene or alkyl vinylidene group or mixtures thereof,    provided that the olefin employed is not the same as the olefin    employed in (i)(b);

Suitable 1-olefins, comprise about 2 to 40 carbon atoms, preferably fromabout 8 to about 30 carbon atoms, such as decene, dodecene, octadeceneand mixtures of C₂₀-C₂₄-1-olefins and C₂₄₋C₂₈-1-olefins. Preferably1-olefins, which are also known as alpha olefins, with number averagemolecular weights in the range of from about 28 to about 560 arepreferred, with molecular weights in the range of from about 112 toabout 420 being more preferred. For example, alpha olefins obtained fromthe thermal cracking of paraffin wax may be employed. Generally, theseolefins range from about 5 to about 20 carbon atoms in length. Anothersource of alpha olefins is the ethylene growth process which gives evennumber carbon olefins. Another source of olefins is by the dimerizationof alpha olefins over an appropriate catalyst such as the well knownZiegler catalyst. Internal olefins are easily obtained by theisomerization of alpha olefins over a suitable catalyst such as silica.Preferably, 1-olefins from C₁₀-C₃₀ are used because these materials arecommercially readily available, and because they offer a desirablebalance of the length of the molecular tail, and the solubility of theterpolymer in nonpolar solvents. Mixtures of olefins are also suitable.

Preparation of Copolymer (i)

Copolymer reactant (i) may be prepared from well known methods which aredescribed in the art including, but not limited to, those methods whichare disclosed in the following patents, which are herein incorporated byreference: Harrison et al., U.S. Pat. No. 5,792,729; Günther et al.,U.S. Pat. No. 6,284,716; and Günther et al., U.S. Pat. No. 6,512,055.

In one embodiment of the present invention the copolymer reactant is apolyalkenyl succinic anhydride terpolymer. These terpolymers arecomposed of at least one of monomers (a) to (c) as described herein.

Typically, the terpolymers of this invention contain at least onemonomer from each group (a) to (c). In general, these components reactto form terpolymers which can be random terpolymers or alternatingterpolymers or block terpolymers and can be prepared by known proceduresfor making copolymers. Additionally, it is possible to form a smallpercentage of copolymers which are composed of monomers (a) and (b) andmonomers (a) and (c). Component (a); the monocarboyxlic acid or esterthereof or dicarboxylic acid or anhydride or ester thereof, us selectedfrom those disclosed above, preferably maleic anhydride. Component (b),the 1-olefin or polyolefin, is preferably polybutene. Component (c), themono-olefin, is preferably a linear alpha olefin containing from about12 to 18 carbon atoms.

The degree of polymerization of the terpolymers can vary over a widerange. Preferably, the degree of polymerization is from about 2 to about10. In general, terpolymer degree of polymerization decreases, as thepolymerization temperature increases.

The terpolymerization is conducted in the presence of a suitable freeradical initiator. Examples of suitable polymerization, initiators areperoxide compounds, such as tertbutyl perpivalate tertbutylpemeocecanoate, tert-butylperethylhexanoate, tertbutylperisobutyrate,di-tert-butyl peroxide, di-tert-amyl peroxide, diacetyl peroxydicaronateand dicyclohexyldicaronate, or azo compounds, such as2,2′-azobisisobutyrontrile. The initiators may be used alone or as amixture with one another. Redox co-initiators may also be present.Preferably, the initiator is a peroxide type initiator, e.g.,di(t-butyl) peroxide, dicumyl peroxide or azo type initiator, e.g.,isobutylnitrile type initiators. Procedures for preparing poly 1-olefincopolymers are, for example, described in U.S. Pat. Nos. 3,560,455 and4,240,916, hereby incorporated by reference in their entirety. Thoseprocedures could be used to prepare terpolymers. Both patents alsodescribe a variety of initiators.

Copolymer (i), wherein a second olefin is employed in the reaction, canbe prepared in the same manner as copolymer (ii) which is describedbelow.

Copolymer (ii)

In another embodiment of the present invention, the copolymer reactantis a copolymer obtained by reacting (a) at least one monoethylenicallyunsaturated C₃-C₂₈ monocarboxylic acid or ester thereof, or a C₄-C₂₈dicarboxylic acid, anhydride or ester thereof and (b) at least onecopolymerizable polymer composed of at least 3 olefin molecules ofpropene or of a branched 1-olefin of from about 4 to about 10 carbonatoms, having a number average molecular weight M_(n) of from about 112to about 5000, and having a terminal copolymerizable group in the formof a vinyl, vinylidene or alkyl vinylidene group in the presence of afree radical initiator.

Thus, preferred copolymers of the present invention are prepared byreacting a “reactive” high molecular weight olefin in which a highproportion of unsaturation, at least about 20% is in the alkylvinylideneconfiguration, e.g.,

wherein R₈ and R₉ are an alkyl or substituted alkyl of sufficient chainlength to give the resulting molecule stability in lubricating oils andfuels, thus R₈ generally has at least about 30 carbon atoms, preferablyat least about 50 carbon atoms and R₉ is a lower alkyl of from about 1to about 6 carbon atoms, with an unsaturated acidic reactant in thepresence of a free radical initiator.

Typically, the copolymer product has alternating polyalkylene andsuccinic groups and has an average degree of polymerization of 1 orgreater.

The preferred copolymers (ii) of the present invention have; the generalformula:

wherein W′ and Z′ are independently selected from the group consistingof —OH; —O-alkyl or taken together are —O— to form a succinic anhydridegroup, n is one or greater; and R₁, R₂, R₃ and R₄ are selected fromhydrogen, alkyl of from about 1 to about 40 carbon atoms, and highmolecular weight polyalkyl wherein either R₁ and R₂ are hydrogen and oneof R₃ and R₄ is lower alkyl haying from about 1 to about 6 carbon atomsand the other is high molecular weight polyalkyl, or R₁ and R₄ arehydrogen and one of R₁ and R₂ is lower alkyl haying from about 1 to 6carbon atoms and the other is high molecular weight polyalkyl.

Copolymer (ii) may be alternating, block or random.

In a preferred embodiment, when maleic anhydride is used as thereactant, the reaction produces copolymers predominately of thefollowing formula:

wherein n is from about 1 to about 100, preferably from about 2 to about20, more preferably from about 2 to about, 10, and R₁, R₂, R₃ and R₄ areselected from hydrogen, lower alkyl of from about 1 to about 6 carbonatoms and higher molecular weight polyalkyl, wherein either R₁ and R₂are hydrogen and one of R₃ and R₄ is lower alkyl having from about 1 toabout 6 carbon atoms and the other is high molecular weight polyalkyl orR₃ and R₄ are hydrogen and one of R₁ and R₂ is lower alkyl and the otheris high molecular weight polyalkyl.

Preferably, the high molecular weight polyalkyl group has at least about30 carbon atoms (more preferably at least about 50 carbon atoms).Preferred high molecular weight polyalkyl groups include polyisobutylgroups. Preferred polyisobutyl groups include those having numberaverage molecular weights, of from about 500 to about 5000, morepreferably from about 900 to about 2500. Preferred lower alkyl groupsinclude methyl and ethyl; especially preferred lower alkyl groupsinclude methyl.

A particularly preferred class of olefin polymers comprises thepolybutenes, which are prepared by polymerization of isobutene. Thesepolybutenes are readily available commercial materials well known tothose skilled in the art. Disclosures thereof will, be found, forexample, in U.S. Pat. Nos. 4,152,499 and 4,605,808, which are hereinincorporated by reference for their disclosures of suitable polybutenes.

Preferably, 1,1-disubstituted olefins are used to provide a highmolecular weighty oil soluble tail in the terpolymer. Preferably the1,1-disubstituted olefin has a number average M_(n) of from about 500 toabout 5000. One particularly useful 1,1-disubstituted olefin is a1,1-disubstituted polyisobutyl ene, such as methyl vinylidenepolyisobutylene.

Preferably the copolymerizable polymer comprises a high molecular weightpolyalkyl group which is derived from a high molecular weight olefin.The high molecular weight olefins used in the preparation of thecopolymers of the present invention are; of sufficiently long chainlength so that the resulting composition is soluble in and compatiblewith mineral oils, fuels; and the like; and the alkylvinylidene isomerof the high molecular weight, olefin comprises at least about 20% of thetotal olefin composition. Preferably, the alkyl vinylidene isomercomprises at least 50%, more preferably at least 70%, of the totalolefin composition.

Such high molecular weight olefins are generally mixtures of moleculeshaying different molecular weights and can have at least one branch per6 carbon atoms along the chain, preferably at least one branch per 4carbon atoms along, the chain, and particularly preferred that there beabout one branch per 2 carbon atoms along, the chain. These branchedchain olefins may conveniently comprise polyalkenes prepared by thepolymerization of olefins of from about 3 to about 6 carbon atoms, andpreferably from olefins of from about 3 to about 4 carbon atoms, andmore preferably from propylene or isobutylene. Theaddition-polymerizable olefins employed are normally 1-olefins. Thebranch may be of from about 1 to about 4 carbon atoms, more usually offrom about 1 to about 2 carbon atoms and preferably methyl.

The preferred alkylvinylidene isomer comprises a methyl- orethylvinylidene isomer, more preferably the methylvinylidene isomer.

The especially preferred high molecular weight olefins used to preparethe copolymers of the present invention are poly is which comprise atleast about 20% of the more reactive methylvinylidene isomer, preferablyat least about 50% and more preferably at least about 70%. Suitablepolyisobutenes include those prepared using BF₃ catalysis. Thepreparation of such polyisobutenes in which the methylvinylidene isomercomprises a high percentage of the total composition is described inU.S. Pat. Nos. 4,152,499 and 4,605,808.

Preparation of Copolymer (ii)

As noted above, copolymer (ii) of the present invention is prepared byreacting an olefin and an unsaturated acidic reactant in the presence ofa free radical initiator. The process of the preparation of copolymer(ii) is described in Harrison, U.S. Pat. No. 5,112,507, which is hereinincorporated by reference in its entirety.

The reaction may be conducted at a temperature of about −30° C. to about210° C., preferably from about 40° C. to about 1.60° C. The degree ofpolymerization is inversely proportional to temperature. Accordingly,for the preferred high molecular weight copolymers, it is advantageousto employ lower reaction temperatures.

The reaction may be conducted neat, that is, both the high molecularweight olefin, acidic reactant and the free radical initiator arecombined in the proper ratio, and then stirred at the reactiontemperature.

Alternatively, the reaction may be conducted in a solvent. Suitablesolvents include those in which the reactants and free radical initiatorare soluble and include acetone, tetrahydrofuran, chloroform, methylenechloride, dichloroethane, toluene, dioxane, chlorobenzene, xylenes, orthe like. After the reaction is complete, volatile components may bestripped off. When a solvent is employed, it is preferably inert to thereactants and products formed and is generally used in an amountsufficient to ensure efficient mixing.

Alternatively, the reaction may be conducted in a diluent, such asmineral oil, as long as the diluent does not contain constituents thatinterfere with the free radical polymerization, e.g., sulfur compounds,antioxidants and the like.

In general, the copolymerization can be initiated by any free radicalinitiator. Such initiators are well known in the art. However, thechoice of free radical initiator may be influenced by the reactiontemperature employed.

The preferred free-radical initiators are the peroxide-typepolymerization initiators and the azo-type polymerization initiators.Radiation can also be used to initiate the reaction, if desired.

The peroxide-type free-radical initiator can be organic or inorganic,the organic having the general formula: R₁₂OOR₁₃ where R₁₂ is anyorganic radical and R₁₃ is selected from the group consisting ofhydrogen and any organic radical. Both R₁₂ and R₁₃ can be organicradicals, preferably hydrocarbon, aryl, and acyl radicals, carrying, ifdesired, substituents such as halogens, etc. Preferred peroxides includedi-tert-butyl peroxide, dicumyl peroxide, and di-tert-amyl peroxide.

Examples of other suitable peroxides, which in no way are limiting,include benzoyl peroxide, lauroyl peroxide; other tertiary butylperoxides; 2,4-dichlorobenzoyl peroxide, tertiary butyl hydroperoxide;cumene hydroperoxide; diacetyl peroxide; acetyl hydroperoxide;diethylperoxycarbonate; tertiary butyl perbenzoate; and the like.

The azo-type compounds, typified by alpha,alpha′-azobisisobutyronitrile,are also well-known free-radical promoting materials. These azocompounds can be defined as those having present in the molecule group—N═N— wherein the balances are satisfied by organic radicals, at leastone of which is preferably attached to a tertiary carbon. Other suitableazo compounds include, but are not limited to, p-bromobenzenediazoniumfluoroborate; p-tolyldiazoaminobenzene; p-bromobenzenediazoniumhydroxide; azomethane and phenyldiazonium halides. A suitable list ofazo-type compounds can be found in U.S. Pat. No. 2,551,813, issued May8, 1951 to Paul Pinkney.

The amount of initiator to employ, exclusive of radiation, of course,depends to a large extent on the particular initiator chosen, the highmolecular olefin used and the reaction conditions. The usualconcentrations of initiator are between 0.001:1 and 0.2:1 moles ofinitiator per mole of acidic reactant, with preferred amounts between0.005:1 and 0.10:1.

The polymerization temperature must be sufficiently high to break downthe initiator to produce the desired free-radicals. For example, usingbenzoyl peroxide as the initiator, the reaction temperature can bebetween about 75° C. and about 90° C., preferably between about 80° C.and about 85° C. higher and lower temperatures can be employed, asuitable broad range of temperatures being between about 20° C. andabout 200° C., with preferred temperatures between about 50° C. andabout 150° C.

The reaction pressure should be sufficient to maintain the solvent inthe liquid phase. Pressures can therefore vary between about atmosphericand 100 psig or higher.

The reaction time is usually sufficient to result in the substantiallycomplete conversion of the acidic reactant and high molecular weightolefin to copolymer. The reaction time is suitable between one and 24hours, with preferred reaction times between 2 and 10 hours.

As noted above, the subject reaction is a solution-type polymerizationreaction. The high molecular weight olefin, acidic reactant, solvent andinitiator can be brought together in any suitable manner. The importantfactors are intimate contact of the high molecular weight olefin andacidic reactant in the presence of a free-radical producing material.The reaction, for example, can be conducted in a batch system where thehigh molecular weight olefin is added all initially to a mixture ofacidic reactant, initiator and solvent or the high molecular weightolefin can be added intermittently or continuously to the reactor.Alternatively, the reactants may be combined in other orders; forexample, acidic reactant and initiator may be added to high molecularweight olefin in the reactor. In another manner, the components in thereaction mixture can be added continuously to a stirred reactor withcontinuous removal of a portion of the product to a recovery train or toother reactors in series. In yet another manner, the reaction may becarried out in a batch process, wherein the high molecular weight olefinis added initially to the reactor, and then the acidic reactant and theinitiator are added gradually over time. The reaction can also suitablytake place in a tubular-type reactor where the components are added atone or more points along the tube.

Copolymer (iii)

In one embodiment, copolymer reactant (iii) is obtained by a copolymerobtained by (a) reacting compound (i)(a) with compound (i)(b) or (i)(c)in a non-free radical catalyzed reaction in the presence of copolymer(i) or copolymer (ii) or both; or by (b) contacting copolymer (i) orcopolymer (ii) or both with the non-free radical catalyzed reactionproduct of compound (i)(a) and compound (i)(b) or (i)(c).

Preparation of Copolymer (iii)

A process for the preparation of copolymer (iii) is described, forexample, in Harrison, et al., U.S. Pat. No. 6,451,920, which is hereinincorporated by reference in its entirety.

In process step (a) above, any unreacted olefin, generally the morehindered olefins, i.e., the beta-vinylidene, that do not react readilywith the monoethylenically unsaturated C₃-C₂₈ monocarboxylic acid orester thereof, or C₄-C₂₈ dicarboxylic acid or an anhydride or esterthereof, under free radical conditions, are reacted withmonoethylenically unsaturated C₃-C₂₈ monocarboxylic acid or esterthereof, or C₄-C₂₈ dicarboxylic acid or an anhydride or ester thereof,under thermal conditions, i.e., at temperatures of from about 180° C. toabout 280° C. These conditions are similar to those used for preparingthermal process PIBSA. Optionally, this reaction takes place in thepresence of a strong acid, such as sulfonic acid. See for example U.S.Pat. No. 6,156,850.

Optionally, a solvent may be used to dissolve the reactants. Thereaction solvent must be one which dissolves both the acidic reactantand the high molecular weight olefin. It is necessary to dissolve theacidic reactant and high molecular weight olefin so as to bring theminto intimate contact in the solution polymerization reaction. It hasbeen found that the solvent must also be one in which the resultantcopolymers are soluble.

Suitable solvents include liquid saturated or aromatic hydrocarbonshaving from about 6 to about 20 carbon atoms; ketones having from about3 to about 5 carbon atoms; and liquid saturated aliphatic dihalogenatedhydrocarbons having from about 1 to about 5 carbon atoms per molecule,preferably from about 1 to about 3 carbon atoms per molecule. By“liquid” is meant liquid under the conditions of polymerization. In thedihalogenated hydrocarbons, the halogens are preferably on adjacentcarbon atoms. By “halogen” is meant F, Cl and Br. The amount of solventmust be such that it can dissolve the acidic reactant and high molecularweight olefin in addition to the resulting copolymers. The volume ratioof solvent to high molecular weight olefin is suitably between 1:1 and100:1 and is preferably between 1.5:1 and 4:1.

Suitable solvents include the ketones having from about 3 to about 6carbon atoms and the saturated dichlorinated hydrocarbons having fromabout 1 to about 5, more preferably from about 1 to about 3, carbonatoms.

Examples of suitable solvents include, but are not limited to:

-   1. ketones, such as: acetone; methylethylketone; diethylketone; and    methylisobutylketone;-   2. aromatic hydrocarbons, such as: benzene; xylene; and toluene;-   3. saturated dihalogenated hydrocarbons, such as: dichloromethane;    dibromomethane; 1-bromo-2-chloroethane; 1,1-dibromoethane;    1,1-dichloroethane; 1,2-dichloroethane; 1,3-dibromopropane;    1,2-dibromopropane; 1,2-dibromo-2-methylpropane;    1,2-dichloropropane; 1,1-dichloropropane; 1,3-dichloropropane;    1-bromo-2-chloropropane; 1,2-dichlorobutane; 1,5-dibromopentane; and    1,5-dichloropentane; or-   4. mixtures of the above, such as: benzenemethylethylketone.

The copolymer is conveniently separated from solvent and any unreactedacidic reactant by conventional procedures such as phase separation,solvent distillation, precipitation and the like. If desired, dispersingagents and/or co-solvents may be used during the reaction.

The polyisobutenyl succinic anhydride (PIBSA), which may be directlyadded to copolymer reactant (i) or (ii), is generally prepared by anumber of well-known processes including the method disclosed within.For example, there is a well-known thermal process (see, e.g., U.S. Pat.No. 3,361,673), an equally well-known chlorination process (see e.g.,U.S. Pat. No. 3,172,892), a combination of the thermal and chlorinationprocesses (see, e.g., U.S. Pat. No. 3,912,764), catalytic strong acidprocesses (see, e.g., U.S. Pat. Nos. 3,819,660 and 6,156,850), and freeradical processes (see, e.g., U.S. Pat. Nos. 5,256,799 and 5,319,030).Such compositions include one-to-one monomeric adducts (see, e.g., U.S.Pat. Nos. 3,219,666 and 3,381,022), as well as high succinic ratioproducts, adducts haying alkenyl-derived substituents adducted with atleast 1.3 succinic groups per alkenyl-derived substituent (see, e.g.,U.S. Pat. No. 4,234,435).

Polyalkylene succinic anhydrides also can be produced thermally alsofrom high methylvinylidene polybutene as disclosed in U.S. Pat. No.4,152,499. This process is further discussed in U.S. Pat. No. 5,241,003for the case where the succinic ratio is less than 1.3 and in EP 0 355895 for the case where the succinic ratio is greater than 1.3. EuropeanApplications EP 0 602 863 and EP 0 587 381, and U.S. Pat. No. 5,523,417disclose a procedure for washing out the polymaleic anhydride resin frompolyalkylene succinic anhydride prepared from high methylvinylidenepolybutene. A polyalkylene succinic anhydride with a succinic ratio of1.0 is disclosed. One advantage of polyalkylene succinic anhydride fromhigh methylvinylidene polybutene is that it can be prepared essentiallyfree of chlorine. U.S. Pat. No. 4,234,435 teaches a preferredpolyalkene-derived substituent group with a number average (M_(n)) inthe range of from about 1500 to about 3200. For polybutenes, anespecially preferred number average (M_(n)) range is from about 17.00 toabout 2400. This patent also teaches that the succinimides must have asuccinic ratio of at least 1.3. That is, there should be at least 1.3succinic groups per equivalent weight of polyalkene-derived substituentgroup. Most preferably, the succinic ratio should be from 1.5 to 2.5.

Other suitable alkenyl succinic anhydrides includes those described inU.S. Pat. No. 6,030,930. Typical alkenyl used in the preparation areethylene and 1-butene copolymers.

(B) The Polyether Aromatic Compound

In one embodiment of the present invention, the copolymer is reactedwith a polyether aromatic compound.

Typically, the polyether aromatic compound will have at least twofunctional groups, each capable of reacting with a monocarboxylic acidor ester thereof, or dicarboxylic acid, anhydride or ester thereof, ormixtures thereof.

Suitable polyether aromatic compounds include, but are not limited to,the following:

Polyether Aromatic Compounds Derived from an Aromatic Aminic Compound

In one embodiment the polyether aromatic compound is derived from anaromatic compound containing at least one amine group and wherein thepolyether is capable of reacting with a monocarboxylic acid or esterthereof, or dicarboxylic acid, anhydride or ester thereof.

Examples of suitable polyether aromatic amines include compounds havingthe following structure:

in which A represents an aromatic aminic moiety wherein the ether groupsare linked through at least one amine group on the aromatic moiety; R₁and R₆ are independently hydrogen, alkyl, alkaryl, aralkyl, or aryl ormixtures; thereof; R₂, R₃, R₄, and R₅ are independently hydrogen oralkyl containing from about 1 to about 6 carbon atoms of mixturesthereof; and a and x are independently integers from about 1 to about50.

in which A represents an aromatic aminic moiety wherein the ethergroups, are linked through at least one aminic functionality on thearomatic moiety; R₁ and R₂ are independently hydrogen, alkyl, aralkyl,or aryl or mixtures thereof; a and b are independently integers fromabout 1 to about 50; and x and y are independently integers from 1 to 4.

in which A represents an aromatic aminic moiety wherein the ether groupsare linked through at least one aminic functionality on the aromaticmoiety; R₁ and R₆ are independently hydrogen, alkyl, alkaryl, aralkyl,or aryl or mixtures thereof; R₂, R₃, R₄, and R₅ are independentlyhydrogen or alkyl containing from about 1 to about 6 carbon atoms ormixtures thereof; a and b are independently an integer from 1 to 4; andx and y are independently integers from about 1 to about 50; and m and nare independently integers from about 1 to about 50.

Furthermore, in one embodiment of the present invention, the polyetheraromatic amine, wherein the polyether is capable of reacting with amonocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride orester thereof, can be a random, block, or alternating copolymer.

A general procedure for preparing polyether hydrocarbylamines can befound, for example, in U.S. Pat. No. 4,847,417.

In general, the polyether aromatic amines employed in this invention maybe synthesized by reacting an aromatic amine compound, such as aniline,with an alkylene oxide compound to form polyether groups on a primary orsecondary nitrogen(s) of the aromatic amine compound, e.g., aniline.Ethylene or propylene carbonate can also, be used to form polyethergroups on the primary or secondary nitrogen(s) of the aromatic aminecompound. The terminal hydroxyl groups of the polyether moieties can beconverted to amino groups via reductive amination or cyanoalkylation,utilizing techniques well known in the art.

in which R₁, R₂, R₃, and R₄ are independently hydrogen or alkylcontaining from about 1 to 6 carbon atoms or mixtures thereof.

Examples of other aromatic amines which may be used in the presentinvention to synthesize suitable polyether aromatic amines include thefollowing:

-   (a) an N-arylphenylenediamine represented by the formula:

-   -   R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain        hydrocarbyl radical having from about 4 to about 24 carbon atoms        selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl;        R(2)₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl,        —CH₂-aryl-NH₂, in which n and m each have a value from about 1        to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl,        aralkyl, or alkaryl, having from about 4 to about 24 carbon        atoms.    -   Particularly preferred N-arylphenylenediamines are        N-phenylphenylenediamines (NPPDA), for example,        N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylenediamine,        and N-phenyl-1,2-phenylenediamine and        N-naphthyl-1,4-phenylenediamine. Other derivatives of NPPDA may        also be included, such as N-propyl-N′-phenylphenylenediamine.

-   (b) aminocarbazole represented by the formula:

-   -   in which R₂₁ and R₂₂ each independently represent hydrogen or an        alkyl or alkenyl radical having from about 1 to about 14 carbon        atoms,

-   (c) an amino-indazolinone represented by the formula:

-   -   in which R₂₃ is hydrogen or an alkyl radical having from about 1        to about 14 carbon atoms; and

-   (d) an aminomercaptotriazole represented by the formula:

-   (e) an aminoperimidine represented by the formula:

-   -   in which R₂₄ represents hydrogen or an alkyl radical having from        about 1 to about 14 carbon atoms;

-   (f) an aryloxyphenyleneamine represented by the formula

-   -   in which R₂₅ is H, —NHaryl, —NHalkaryl, or branched or straight        chain radical having from about 4 to about 2.4 carbon atoms that        can be alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₂₆ is —NH₂,        —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, or —NHaralkyl, in which n and m        each have a value from about 1 to about 10; and R₂₇ is hydrogen,        alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, haying from about        4 to about 24 carbon atoms; provided that when R₂₅ is hydrogen        of a branched or straight chain radical having from about 4 to        about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl,        aralkyl of alkaryl, then R₂₆ must be NH₂ or        —(NH(CH₂)_(n))_(m)NH₇, —CH₂—(CH₂)_(n)—NH₂, or —CH₂-aryl-NH₂.

A particularly preferred aryloxyphenyleneamine is 4-phenoxyaniline;

-   (g) an aromatic amine comprising two aromatic groups, linked by a    group, L, represented by the following formula:

-   -   wherein L is selected from —O—, —N═N—, —NH—, —CH₂NH, —C(O)NR₂₈—,        —C(O)O—, —SO₂—, —SO₂NR₂₉— or —SO₂NH—, wherein R₂₈ and R₂₉        independently represent a hydrogen, an alkyl, an alkenyl or ah        alkoxy group having from about 1 to about 8 carbon atoms;    -   wherein each Y₁, Y₂, Y₃ and Y₄ are independently N or CH        provided that Y₁ and Y₂ may not both be N;    -   R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl,        alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂,        —SO₃H, —SO₃Na, CO₂H or salt thereof, —NR₄₁R₄₂ wherein R₄₁ and        R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or        alkaryl;    -   R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an        alkenyl or an alkoxy group having from about 1 to about 8 carbon        atoms, —OH, —SO₃H or —SO₃Na;    -   R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an        alkenyl group having from about 1 to about 8 carbon atoms,        —CH₂—(CH₂)_(n)—NH₂ or —CH₂— aryl-NH₂ and n is from 0 to about        10;    -   provided that when R₃₄ is —NHR₃₅ wherein R₃₅ is ah alkyl or an        alkenyl group having from about 1 to about 8 carbon atoms, then        either L is —NH— or —CH₂—NH—; or R₃₀ or R₃₁ is OH or —NR₄₁R₄₂        wherein at least one of R₄₁ or R₄₂ is hydrogen; or R₃₂ or R₃₃ is        OH.

-   (h) an aminothiazole selected from the group consisting of    aminothiazole, aminobenzothiazole, aminobenzothiadiazole and    aminoalkylthiazole;

-   (i) an aminoindole represented by the formula:

-   -   wherein R₃₆ represents a hydrogen, an alkyl or an alkenyl group        having from about 1 to about 14 carbon atoms;

-   (j) an aminopyrrole represented by the formula:

-   -   wherein R₃₇ represents a divalent alkylene group having about 2        to about 6 carbon atoms and R₃₈ represents a hydrogen, an alkyl        or an alkenyl group having from about 1 to about 14 carbon        atoms;

-   (k) a ring substituted or unsubstituted aniline, such as    nitroaniline or 4-aminoacetanilide;

-   (l) an aminoquinoline;

-   (m) an aminobenzimidazole;

-   (n) a N, N-dialkylphenylenediamine; and

-   (o) a benzylamine.

Polyether Aromatic Compounds Derived from an Aromatic CompoundContaining, at Least Two Hydroxyl Groups

In one embodiment, the polyether aromatic compound is a polyetheraromatic compound which is derived from an aromatic compound containingat least two hydroxyl groups and wherein the polyether is capable ofreacting with a monocarboxylic acid or ester thereof, or dicarboxylicacid, anhydride or ester thereof. In general, the polyether aromaticcompound employed in this invention may be synthesized by reacting anaromatic compound containing at least two hydroxyl groups, such ashydroquinone or resorcinol, with an alkylene oxide compound to formpolyether groups off the hydroxyl groups. Ethylene, or propylenecarbonate can also be used to form polyether groups off the hydroxylgroups. The terminal hydroxyl groups of the polyether moieties can beconverted to amino groups via reductive animation or cyanoalkylation,utilizing techniques well known in the art.

Examples of suitable polyether aromatic hydroxyl compounds includecompounds having the following structures:

In which R₁, R₂, R₃, and R₄ are independently hydrogen or alkylcontaining from about 1 to about 6 carbon atoms or mixtures thereof; andx and y are independently integers from about 1 to about 50.

in which R₁ and R₆ are independently hydrogen, alkyl, alkaryl, aralkyl,or aryl or mixtures thereof; R₂, R₃, R₄, and R₅ are independentlyhydrogen or alkyl containing from about 1 to about 6 carbon atoms ormixtures thereof; and x and y are independently integers from about 1 toabout 50.

Typically, these compounds include polyether bisphenol-A, polyethercatechol, polyether hydroquinone, and polyether resorcinol.

Polyether Aromatic Compounds Derived from Aromatic Compounds Haying atLeast One Amine Group and at Least One Hydroxyl Group

In another embodiment of the present invention, the polyether aromaticcompound is derived from an aromatic compound having at least one aminegroup and at least one hydroxyl group. In general, the polyetheraromatic compound employed in this invention may be synthesized byreacting an aromatic compound containing at least one hydroxyl group andat least one amine group such as 4-aminophenol, with an alkylene oxidecompound to form polyether groups off the hydroxyl group(s) and/or aminogroup(s). Ethylene or propylene carbonate can also be used to formpolyether groups off the hydroxyl group(s) and/or amino group(s). Theterminal hydroxyl group(s) of the polyether moieties can be converted toamino groups via reductive animation or cyanoalkylation, utilizingtechniques well known in the art.

In which R₁, R₂, R₃, and R₄ are independently hydrogen or alkylcontaining from about 1 to about 6 carbon atoms or mixtures thereof; R₅is hydrogen, alkyl, aryl, alkaryl, or aralkyl; and x and y areindependently integers from about 1 to about 50.

(C) The Polyether Aliphatic Compound

In one embodiment of the present invention, the copolymer is alsoreacted with a polyether aliphatic compound.

Typically, the polyether aliphatic compound will have at least twofunctional groups; each capable of reacting with a monocarboxylic acidor ester thereof, or dicarboxylic acid, anhydride or ester thereof.

Suitable polyether aliphatic compounds include, but are not limited to,the following:

Polyether Aliphatic Amines

Polyether aliphatic compound having at least two functional groups, eachcapable of reacting with a monocarboxylic acid of ester thereof, ordicarboxylic acid, anhydride or ester thereof.

An example of a polyether aliphatic compound is a polyoxyethylene aminehaving the following structure:

A general procedure for preparing polyether hydrocarbylamines can befound, for example, in U.S. Pat. No. 4,847,417, the disclosure of whichis incorporated by reference herein.

In another embodiment, the polyether aliphatic amine employed in thepresent invention may be the by-product of reductive animation of apolyether containing, hydroxyl termini. For example, when apolyoxyethylene oxide glycol, e.g. triethyleneoxide glycol, isreductively aminated to convert the hydroxyl end groups to amines,dialkylation of nitrogen can occur to form to dimers, trimers, andhigher oligomers as shown in the following schematic.

However, in general, the polyether aliphatic amines employed in thisinvention may be synthesized by reacting an aliphatic amine compound,such as tertiary butyl amine, with an alkylene oxide compound to formpolyether groups on a primary or secondary nitrogen(s) of the aliphaticamine, compound, e.g., t-butyl amine. Ethylene or propylene carbonatecan also be used to form polyether groups on the primary or secondarynitrogen(s) of the aliphatic amine compound. The terminal hydroxylgroups of the polyether moieties can be converted to amino groups viareductive amination or cyanoalkylation, utilizing techniques well knownin the art.

in which R₁, R₂, R₃, and R₄ are independently hydrogen or alkylcontaining from about 1 to 6 carbon atoms or mixtures thereof.

Examples of other aliphatic amines which may be used in the presentinvention to synthesize suitable polyether aliphatic amines include thefollowing: dimethylaminopropylamine, diethylyaminopropylamine, dibutylaminopropyl amine, dimethylaminoethylamine, diethylaminoethylamine,dibutylaminoethylamine, 1-(2-aminoethyl) piperidine,1-(2-aminoethyl)pyrrolidone, aminoethylmorpholine, andaminopropylmorpholine. Preferably, the aliphatic amine having a singlereactive amino group is N,N-dimethylaminopropylamine oraminopropylmorpholine. For example, a polyoxyethylene aliphatic aminederived from N,N-dimethylaminopropylamine is represented by thefollowing structure.

Polyether Aliphatic Amino Hydroxyl Compounds

In another embodiment of the present invention, the polyether aliphaticcompound may be a polyether aromatic amino hydroxyl compound. Ingeneral, the polyether aromatic amino hydroxyl compound employed in thisinvention may be synthesized by reacting an aromatic compound containingat least one hydroxyl group and at least one amino group, such asethanol amine, with an alkylene oxide compound to form polyether groupsoff the hydroxyl group(s) and/or amino group(s). Ethylene or propylenecarbonate can also be used to form polyether groups off the hydroxylgroup(s) and/or amino group(s). The terminal hydroxyl group(s) of mepolyether moieties can be converted to amino groups via reductiveanimation or cyanoalkylation, utilizing techniques well known in theart.

For example, a polyoxyethylene aliphatic amine derived from ethanolamineis represented by the following structures:

In one embodiment of the present invention, the copolymer is furtherreacted with an ether compound capable of linking two succinimidegroups. One suitable ether compound includes, but is not limited to, thefollowing:

Polyether Aliphatic Amines

Typically, the polyether polyaliphatic amine compound employed in thepresent invention is synthesized according to the description in U.S.Pat. No. 4,847,417 which is herein incorporated in its entirety byreference.

Generally, the copolymer may be reacted with polyether polyaliphaticamine compounds. Optionally, the copolymer is also reacted with amixture of polyether polyamines, polyether amino alcohols, polyetheramino thiols, polyether polyols, or ether diamines to form a mixture ofimides, amides and esters.

(D) Additional Reactants

Optionally, in addition to the ether compounds (i.e. polyether aromatic;compound and polyether aliphatic compound) above, the copolymer may alsobe reacted with (1) at least one ether compound as defined herein; (2)at least one aromatic compound capable of reacting with at least onemonocarboxylic acid or ester thereof; or dicarboxylic acid, anhydride,or ester thereof, or mixtures thereof; or (3) at least one aliphaticcompound capable of reacting with at least one monocarboxylic acid orester thereof; or dicarboxylic acid, anhydride or ester thereof, ormixtures thereof; or mixtures thereof of (1), (2) or (3).

The Ether Compounds

In one embodiment of the present invention, optionally, the copolymerand the polyether aromatic and polyether aliphatic compounds may befurther reacted with an ether compound capable of being reacted with atleast two monocarboxylic acids or esters thereof, or with at least twodicarboxylic acids, anhydrides, or esters thereof, or mixtures thereof.

Suitable ether compounds includes but are not limited to, the following:

Polyether Polyamines

Examples of suitable polyetheramines include compounds having thefollowing structure:

wherein R₁ is independently hydrogen or a hydrocarbyl group having 1 to4 carbons, and n is the degree of polymerization. Generally thepolyether polyamines suitable, for use in the present invention willcontain at least about one ether unit, preferably from about 5 to about100, more preferably from about 10 to 50, and even more preferably fromabout 15 to about 25 ether units.

The polyether polyamines can be based on polymers derived from C₂-C₆epoxides such as ethylene oxide, propylene oxide, and butylene oxide.Examples of polyether polyamines are sold under the Jeffamine® brand andare commercially available from Hunstman Corporation located in Houston,Tex.

Other examples of suitable polyetheramines include polyoxytetramethylenepolyamine compounds having the following structure:

wherein n is the degree of polymerization (i.e., number of monomer etherunits).

Polyether Amine Derivatives

Furthermore, the copolymer reactant may be reacted with a polyetheramino alcohol or amino thiol.

Polyether Amino Alcohol

Typically, amino alcohols may be formed when the alcohol end groups of acompound are not completely converted to amines during reactions, suchas reductive, amination. Also, one may initiate a polymer chain (i.e.grow propylene of ethylene oxide) from an amino group and therefore havean amino on one end of the polymer chain (i.e. initiator) and an alcoholterminus, or an amine internally in the molecule with alcohol termini.

Examples of suitable polyetheramino alcohols include compounds havingthe following structure:

wherein R₁ is independently a hydrogen or hydrocarbyl group, having 1 to4 carbons, and n is the degree of polymerization. Generally, thepolyether amino alcohols, suitable for use in the present invention willcontain at least about one ether unit, preferably from about 5 to about100, more preferably from about 10 to about 50, and even more preferablyfrom about 15 to about 25 ether units.

Other examples of suitable polyetheramino alcohols includepolyoxytetramethyleneamino alcohol compounds having the followingstructure:

wherein n is the degree of polymerization.

Polyether Amino Thiol

Examples of suitable polyetheramino thiols include compounds having thefollowing structure:

wherein R is independently a hydrogen or hydrocarbyl group, having 1 to4 carbons and n is the degree of polymerization.

Other examples of suitable polyetheramino thiols includepolyoxytetramethyleneamino thiol having the following structure:

wherein n is the degree of polymerization.

Generally, the polyetheramino thiols suitable for use in the presentinvention will contain at least about one ether unit, preferably fromabout 5 to about, 100, more preferably from about 10 to about 50, andeven more preferably from about 15 to about 25 ether units.

Ether Polyamines

Ether Diamines

In yet another embodiment of the present invention, the copolymer may bereacted with ether diamines. Suitable diamines are reacted with thecopolymer, such as decyloxypropyl-1,3-diaminopropane,isodecyloxypropyl-1,3-diaminopropane,isododecyloxypropyl-1,3-diaminopropane,dodecyl/tetradecyloxypropyl-1,3-diaminopropane,isotridecyloxypropyl-1,3-diaminopropane,tetradecyloxypropy-1,3-diaminopropane.

Polyether Polyol

In yet another embodiment of the present invention, the copolymer may bereacted with a polyether containing at least two hydroxyl end groups toform an ester. The polyether polyols have the following structure:

wherein R₁ is independently a hydrogen or hydrocarbyl group, having 1 to4 carbons, and n is the degree of polymerization.

Other examples of suitable polyether polyols includepolyoxytetramethylene polyol compounds, such as those referred to asTerathane® which may be purchased from DuPont Corporation, Wilmington,Del., having the following structure:

wherein n is the degree of polymerization.

Suitable polyether polyols include, but are not limited to, thefollowing: polyoxyethylene glycol, polyoxypropylene glycol,polyoxybutylene glycol, and polyoxytetramethylene glycol.

The molecular weight of the presently employed polyether polyol willgenerally range from about 150 to about 5000, preferably from about 500to about 2000.

Generally, the polyether compounds suitable for use in the presentinvention will contain at least one either unit preferably from about 5to about 100, more preferably from about 10 to about 50, and even morepreferred from about 15 to about 25 ether units.

Generally, the polyether compounds suitable for use in the presentinvention may be derived from only one ether type or a mixture of ethertypes, such as poly(oxyethylene-co-oxypropylene) diamine. The mixture ofether units may be block, random, or alternating copolymers. Thepresently employed ether compounds are capable of reacting with at leasttwo carboxylic acid groups or anhydride derivatives thereof.

Generally, the copolymer may be reacted with a mixture of polyetherpolyamines, polyether amino alcohols, polyether amino thiols, polyetherpolyols, or ether diamines to form a mixture of imides, amides andesters.

Aromatic Compounds

Optionally, in addition to the ether compounds (i.e. polyether aromaticcompound and polyether aliphatic compound) above, the copolymer may alsobe reacted with at least one aromatic compound capable of reacting withat least one monocarboxylic acid or ester thereof; or dicarboxylic acid,anhydride or ester thereof.

Preferably, the aromatic compound is selected from the following groupof aromatic compounds consisting of:

-   (a) an N-arylphenylenediamine represented by the formula:

-   -   R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain        hydrocarbyl radical having from about 4 to about 24 carbon atoms        selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl;        R(2)₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl,        —CH₂-aryl-NH₂, in which h and m each have a value from about 1        to about 10; and R is hydrogen, alkyl, alkenyl, alkoxyl,        aralkyl, or alkaryl, having from about 4 to about 24 carbon        atoms.

Particularly preferred N-arylphenylenediamines areN-phenylphenylenediamines (NPPDA), for example,N-phenyl-1,4-phenylenediamine, N-phenyl-1,3-phenylenediamine, andN-phenyl-1,2-phenylenediamine and N-naphthyl-1,4-phenylenediamine. Otherderivatives of NPPDA may also be included, such asN-propyl-N′-phenylphenylenediamine.

-   (b) aminocarbazole represented by the formula:

-   -   in which R₂₁ and R₂₂ each independently represent hydrogen or an        alkyl or alkenyl radical having from about 1 to about 14 carbon        atoms,

-   (c) an amino-indazolinone represented by the formula:

-   -   in which R₂₃ is hydrogen or an alkyl radical having from about 1        to about 14 carbon atoms; and

-   (d) an aminomercaptotriazole represented by the formula:

-   (e) an aminoperimidine represented by the formula;

-   -   in which R₂₄ represents hydrogen or an alkyl radical having from        about 1 to about 14 carbon atoms;

-   (f) an aryloxyphenyleneamine represented by the formula:

-   -   in which R₂₅ is H, —NHaryl, —NHalkaryl, or branched or straight        chain radical having from about 4 to about 24 carbon atoms that        can be alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₂₆ is —NH₂,        —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, or —NHaralkyl, in which n and m        each have a value from about 1 to about 10; and R₂₇ is hydrogen,        alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about        4 to about 24 carbon atoms;

A particularly preferred aryloxyphenyleneamine is 4-phenoxyaniline;

-   (g) an aromatic amine comprising two aromatic groups, linked by a    group, L, represented by the following formula:

-   -   wherein L is selected from —O—, —N═N—, —NH—, —CH₂NH, —C(O)NR₂₈—,        —C(O)O—, —SO₂—, —SO₂NR₂₉— or —SO₂NH—, wherein R₂₈ and R₂₉        independently represent a hydrogen, an alkyl, an alkenyl or an        alkoxy group having from about 1 to about 8 carbon atoms;    -   wherein each Y₁, Y₂, Y₃ and Y₄ are independently N or CH        provided that Y₁ and Y₂ may not both be N;    -   R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl,        alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂,        —SO₃H, —SO₃Na, CO₂H or salt thereof, —NR₄₁R₄₂ wherein R₄₁ and        R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or        alkaryl;    -   R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an        alkenyl or an alkoxy group having from about 1 to about 8 carbon        atoms, —OH, —SO₃H or —SO₃Na;    -   R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an        alkenyl group having from about 1 to about 8 carbon atoms,        —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10;

-   (h) an aminothiazole selected from the group consisting of    aminothiazole, aminobenzothiazole, aminobenzothiadiazole and    aminoalkylthiazole;

-   (i) an aminoindole represented by the formula:

-   -   wherein R₃₆ represents a hydrogen, an alkyl or an alkenyl group        having from about 1 to about 14 carbon atoms;

-   (j) an aminopyrrole represented by the formula:

-   -   wherein R₃₇ represents a divalent alkylene group having about 2        to about 6 carbon atoms and R₃₈ represents a hydrogen, an alkyl        or an alkenyl group having from about 1 to about 14 carbon        atoms;

-   (k) a ring substituted or unsubstituted aniline, such as    nitroaniline or 4-aminoacctanilide;

-   (l) an aminoquinoline;

-   (m) an aminobenzimidazole;

-   (n) a N, N-dialkylphenylenediamine;

-   (o) a benzylamine; and

-   (p) a benzyl alcohol.

The compounds described above in (g)-(o) are substantially described,for example, in Published U.S. Patent Application No, US20060025316, thedisclosure of which is herein incorporated by reference:

The above-described amine compounds can be used alone or in combinationwith each other. Other aromatic amines can include such amines asaminodiphenylamine. These additional amines can be included for avariety of reasons.

In one embodiment, the preferred aromatic amine compound is eitherN-arylphenylenediamine or phenoxyaniline. More preferred, the aromaticamine compound is N-arylphenylenediamine. Particularly preferredN-arylphenylenediamines are the N-phehylphenylenediamines, such as forexample, N-phenyl-1,4-phenylenediamine, N-phenyl-1-phenylenediamine, andN-phenyl-1,2-phenylenediamine.

In one embodiment, the preferred aromatic compound is4-(4-nitrophenylazo)aniline, 4-phenylazoanline, N-(4-aminophenyl)acetamide, 4-benzoylamine-2,5-dimethoxyaniline, 4-phenoxyl aniline, pr3-nitroniline.

Aliphatic Compound

Optionally, in addition to the ether compounds (i.e. polyether aromaticcompound and polyether aliphatic compound) above, the copolymer may alsobe reacted with at least one aliphatic compound capable of reacting withat least one monocarboxylic acid or ester thereof; or dicarboxylic acid,anhydride or ester thereof. Preferably, the aliphatic, compound willcontain one or more amino functional groups or one or more hydroxylfunctional groups or both.

Amino Aliphatic Compound

In addition to the ether compound (i.e. polyether aromatic compound)above, optionally, the copolymer may also be reacted with at least onealiphatic compound which may be an amino aliphatic compound.

The amino aliphatic compound may be selected from the group comprisingof (a) aliphatic monoamines (b) aliphatic diamines, (c) aliphaticpolyamines pr (d) polyalkylene polyamines. Aliphatic monoamines includemethylamine, ethylamine, propylamine and various higher amines. Diaminesor polyamines may also be employed. Preferably, they will have only asingle reactive amino group, that is, a primary or secondary, andpreferably primary group. Suitable examples of diamines includedimethylaminopropylamine, diethylyaminopropylamine, dibutyl aminopropylamine, dimethylaminoethylamine, diethylaminoethylamine,dibutylaminoethylamine, 1-(2-aminoethyl) piperidine,1-(2-aminoethyl)pyrrolidone, aminoethylmorpholine, andaminopropylmorpholine. Preferably, the aliphatic amine having a singlereactive amino group is N,N-dimethylaminopropylamine oraminopropylmorpholine.

Additionally, the amino aliphatic compound could be a polyethercontaining a single amino end group.

Preferably, the polyalkylene polyamine has greater than 4 amine nitrogenatoms per mole, up to a maximum of about 12 amine nitrogen atoms permole. Most preferred are polyamines having from about 5 to about 7nitrogen atoms per mole. The number of amine nitrogen atoms per mole ofpolyamine is calculated as follows:

${{Number}\mspace{14mu}{of}\mspace{14mu}{nitrogen}\mspace{14mu}{atoms}\mspace{14mu}{Per}\mspace{14mu}{mole}\mspace{14mu}{of}\mspace{14mu}{polyamine}} = \frac{\%\mspace{14mu} N \times M_{pa}}{14 \times 100}$

wherein

% N=percent nitrogen in polyamine or polyamine mixture

M_(pa)=number average molecular weight of the polyamine or polyaminemixture

Suitable aliphatic polyamines include polyalkylene polyamines. Preferredpolyalkylene polyamines also contain from about 4 to about 40 carbonatoms, there being preferably from 2 to 3 carbon atoms per alkyleneunit. The polyamine preferably has a carbon-op-nitrogen ratio of fromabout 1:1 to about 10:1.

Examples of suitable include the following: tetraethylene pentamine,pentaethylene hexamine and heavy polyamine, HPA, (available from DowChemical Company, Midland, Mich.). Such amines encompass isomers such asbranched-chain polyamines and the previously mentioned substitutedpolyamines, including hydrocarbyl-substituted polyamines.

When more than one primary or secondary amino group is present, thereaction conditions and/or stoichiometry should be such that oilsolubility is maintained.

Hydroxy Aliphatic Compound

In addition to the ether compound (i.e. polyether aromatic compound)above, optionally, the copolymer may also be reacted with at least onealiphatic compound which may be a hydroxy aliphatic compound.

The mono- or multifunctional hydroxyl compounds used according to theprocess of the present invention may contain primary, secondary ortertiary alcohols.

Suitable hydroxyl aliphatic compounds include, but are not limited to,ethanol, isopropyl alcohol, isobutyl alcohol, tert-butyl alcohol,glycerol and the like. Additionally, the hydroxyl aliphatic compoundcould be a polyether containing a single hydroxyl end group.

The hydroxyl compound may also contain a hetero atom, such as sulfur(e.g., betamercaptoethanol).

Method of Making the Lubricating Oil Additive Composition

The lubricating oil additive composition is prepared by a processcomprising Charging the reactant copolymer (e.g., at least one ofcopolymers (i), (ii) and (iii) as described herein) in a reactor,optionally under a nitrogen purge, and heating at a temperature of fromabout 80° C. to about 170° C. Optionally, diluent oil may be chargedoptionally under a nitrogen purge in the same reactor, thereby producinga diluted copolymer reactant. The amount of diluent oil in the dilutedcopolymer is up to about 80 weight %, more preferred from about 20 toabout 60 weight %, and most preferred from about 30 to about 50 weight%. A polyether aliphatic compound and a polyether aromatic compoundoptionally under a nitrogen purge, to the reactor. Optionally, anaromatic compound capable of reacting with at least one monocarboxylicacid or ester thereof, or dicarboxylic acid, anhydride or ester thereof;an aliphatic compound capable of reacting with at least onemonocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride orester thereof; or both are also charged to the reactor. This mixture isheated under a nitrogen purge to a temperature in range from about 130°C. to about 200° C. Optionally, a vacuum is applied to the mixture forabout 0.5 to about 2.0 hours to remove excess water.

The lubricating oil additive composition can also be made using aprocess comprising simultaneously charging all the reactants (reactantcopolymer (i), (ii), or (iii); and, optionally, the aromatic compound,and optionally the aliphatic compound at the desired ratios into thereactor. One or more of the reactants can be charged at an elevatedtemperature to facilitate mixing and reaction. A static mixer can beused to facilitate mixing of the reactants as they are being charged tothe reactor. The reaction is carried out for about 0.5 to about 2 hoursat a temperature from about 130° C. to about 200° C. Optionally a vacuumis applied to the reaction mixture during the reaction period.

When an aliphatic compound, an aromatic compound or both are employed inthe present invention and when more than one functional group is presenton the compound(s), the reaction conditions and/or stoichiometry shouldbe such that oil solubility is maintained. For example, whenmultifunctional aliphatic compounds, aromatic compounds or both areused, the linker group (i.e., the polyether compound) and the copolymerare preferably charged to the reactor first and allowed to react priorto addition of the multifunctional compounds. Furthermore, thestoichiometry should be such that when the multifunctional aliphaticcompound, aromatic compound or both are charged to the reactor, there isgenerally about one molecule of reactive monoethylenically unsaturatedmono- or dicarboxylic acid functions per molecule of the multifunctionalcompound(s). This reaction order and stoichiometry reduces excessivecrosslinking by limiting the number of unreacted monoethylenicallyunsaturated mono- or dicarboxylic acid sites relative to the number ofreactive sites on the multifunctional aliphatic compound, aromaticcompound or both. Reduction of excessive crosslinking may decrease theprobability of gel formation, and therefore increase the probability ofoil solubility.

In one embodiment of the invention, the non-free radical catalyzedreaction product of compound (i)(a) and compound (i)(b) or (i)(c), whichis contacted with either copolymer (i) or copolymer (ii) or both, may becontacted in the presence of (1) the aromatic compound, (2) thealiphatic compound or both and prior to the addition of component (B)(i.e. the polyaromatic ether compound) and component (C) (i.e. thepolyaliphatic ether compound).

Lubricating Oil Composition

The lubricating oil additive composition described above is generallyadded to abase oil that is sufficient, to lubricate moving parts, forexample internal combustion engines, gears, and transmissions.Typically, the lubricating oil competition of the present inventioncomprises a major amount of an oil of lubricating viscosity and a minoramount of the lubricating oil additive composition.

The base oil employed may be any of a wide variety of oils oflubricating viscosity. The base oil of lubricating viscosity used insuch compositions may be mineral oils or synthetic oils. A base oilhaving a viscosity of at least 2.5 cSt at 40° C. and a pour point below20° C., preferably at of below 0° C., is desirable. The base oils may bederived from synthetic or natural sources.

Mineral oils for use as the base oil in this invention include, forexample, paraffinic, naphthenic and other oils that are ordinarily usedin lubricating oil compositions. Synthetic oils include, for example,both hydrocarbon synthetic oils and synthetic esters and mixturesthereof having the desired viscosity. Hydrocarbon synthetic oils, mayinclude, for example, oils prepared from the polymerization of ethylene,polyalphaolefin or FAQ oils, or oils prepared from hydrocarbon-synthesisprocedures using carbon monoxide and hydrogen gases such as in aFisher-Tropsch process. Useful synthetic hydrocarbon oils include liquidpolymers of alpha olefins having the proper viscosity. Especially usefulare the hydrogenated liquid oligomers of C₆ to C₁₂ alpha olefins such as1-decene trimer. Likewise, alkyl benzenes of proper viscosity, such asdidodecyl benzene, can be used. Useful synthetic esters include theesters of monocarboxylic acids and polycarboxylic acids, as well asmono-hydroxy alkanols and polyols. Typical examples are didodecyladipate; pentaerythritol tetracaproate, di-2-ethylhexyl adipate,dilaurylsebacate, and the like. Complex esters prepared from mixtures ofmono and dicarboxylic acids and mono and dihydroxy alkanols can also beused. Blends of mineral oils with synthetic oils are also useful.

Thus, the base oil can be a refined paraffin type base oil, a refinednaphthenic base oil, or a synthetic hydrocarbon or non-hydrocarbon oilof lubricating viscosity. The base oil can also be a mixture of mineraland synthetic oils.

Method of Use of the Present Invention

The lubricating oil additive composition of the present invention isadded to an oil of lubricating viscosity thereby producing a lubricatingoil composition. The lubricating oil composition contacts the engine,improving dispersancy. Accordingly, the present invention is alsodirected to a method of improving soot dispersancy, sludge dispersancy,or both in an internal combustion engine which comprises operating theengine with the lubricating oil composition of the invention.

Optionally, the lubricating oil additive composition described above maybe used as a fuel additive. When used in fuels, the proper concentrationof the additive that is necessary to achieve the desired detergency isdependent upon a, variety of factors including the type of fuel used,the presence of other detergents or dispersants or other additives, etc.Generally, however, the range of concentration of the additive in thebase fuel is 10 to 10,000 weight parts per million, preferably from 30to 5,000 parts per million of the additive. If other detergents arepresent, a lesser amount of the additive may be used. The additivesdescribed herein may be formulated as a fuel concentrate using an inertstable oleophilic solvent boiling in the range of about 150-400° F.(65.6-204.4° C.). Preferred solvents boil in the gasoline or diesel fuelrange. Preferably, an aliphatic or an aromatic hydrocarbon solvent isused, such as a benzene, toluene, xylene or higher-boiling, aromatics oraromatic thinners. Aliphatic alcohols of about 3 to 8 carbon atoms, suchas isopropanol, isobutylcarbinol, n-butanol and the like in combinationwith hydrocarbon solvents are also suitable for use with the fueladditive. In the fuel concentrate; the amount of the additive will beordinarily at least 5 percent by weight and generally not exceed 70percent by weight, preferably from 5 to 50 and more preferably from 10to 25 weight percent.

The following examples are presented to illustrate specific, embodimentsof this invention and are not to be construed in any way as limiting thescope of the invention.

EXAMPLES Example 1 Preparation of Terpolymer

2513 grams of high methylvinylidene polyisobutylene having a numberaverage molecular weight (Mn) of about 2300 and a methylvinylidenecontent of about 78% (which is available from BASF as Glissopal® 2300)was charged to a 4-L reactor equipped with agitator, temperaturecontroller and overhead condenser and receiver. 27.3 grams 1-hexadecenewas also charged to the reactor, and the agitated mixture, was heated to150° C. Traces of moisture were removed by sparging 250 scm³/minnitrogen through the mixture for about an hour. After drying/thenitrogen was fed to the reactor head space at a rate of 30 scm³/min.178.8 grams maleic anhydride and 16.4 grams dicumyl peroxide in a 50%solution with toluene were fed simultaneously to the reactor over 2hours. After the maleic anhydride and dicumyl peroxide charging werefinished, the temperature of the reactor was maintained at 150° C. foranother 1.5 hours. The reactor was heated to 190° C. During the heatingof the reactor, the pressure was gradually lowered to 2.0 mm Hg when thetemperature of the reactor, reached 180° C. The temperature was held at190° C. and the pressure was held at 20 mm Hg for 1 hour during which 15grams of condensate was collected. The product was cooled and a yield of2693 grams of copolymer (i) was obtained.

Example 2 Preparation of PolyPIBSA (Copolymer (ii))

4005 grams of high methylvinylidene polyisobutene having a numberaverage molecular weight (M_(n)) of about 1000 and a methylvinylidenecontent of about 76% (which is commercially available from BASF and isknown as Glissopal 1000) was charged to a reactor and the reactor washeated to a temperature of about 150° C. 589 grams maleic anhydride and54.14 grams of dicumyl peroxide were fed to the reactor. The temperatureof the reactor was maintained at 150° C. for 1.5 hours after the maleicanhydride and dicumyl peroxide are charged to the reactor. The reactorwas heated to about 200° C. The product was then filtered to provide theneat product.

Example 3 Preparation of Alpha-Olefin/Maleic Anhydride Copolymer

100 parts by weight Exxon 150 solvent (C₁₀ aromatic solvent) and 81.94parts per weight of C₁₄₋₂₄ alpha olefin mixture (average molecularweight—215.3 Daltons) were charged to a stirred reactor. The mixture washeated to 150° C. and the temperature was maintained for about 30minutes to dehydrate the mixture. The mixture was cooled to 65° C., and36.5 parts of maleic anhydride were charged to the reaction mixture. Thereactor headspace was purged with nitrogen. The reaction mixture washeated to 150° C., 0.13 parts of di-tert-butyl peroxide were added tothe reaction mixture. The reactor temperature was allowed to increase(exotherm) to about 180° C. Once the temperature began to decrease(exotherm passed), the reaction mixture was cooled to 150° C. Theperoxide addition step was repeated five more times. After the sixthperoxide addition the reactor was heated to 170° C., and the temperaturewas maintained for one hour. The aromatic solvent was the stripped fromthe product under vacuum, and then approximately 276 parts of 100Nneutral oil were added to the product.

Example 4 Preparation of Thermal PIBSA

The procedure of Preparation 2 in U.S. Pat. No. 5,872,083 ('083 patent)was employed except that 2300 Mn polybutene; available as Glissopal®2300 from BASF, was used instead of 2200 Mn polybutene as used in the'083 patent.

Example 5 Synthesis of polyoxyalkyleneamine derivative ofN-phenyl-1,4-phenylenediamine

A polyoxyalkyleneamine containing both ethylene oxide and propyleneoxide units derived from a N-phenyl-1,4-phenylenediamine (NPPDA) core isa mixture of structures (i) and (ii):

It is contemplated that the reaction product, derived from theN-phenyl-1,4-phenylenediamine (NPPDA), comprises a mixture of structures(i) and (ii). Such a compound is prepared by reacting 15 moles ofethylene oxide and 5 moles of propylene oxide withN-phenyl-1,4-phenylenediamine to form a mixture of polyetherdiol andpolyethertriol. The polyethertriol and polyetherdiol is then reductivelyaminated with ammonia and hydrogen to provide polyethers with terminalaminic groups, wherein the primary aliphatic amine content is 1.91 meqN/g.

Example 6 Synthesis of polyoxyalkyleneamine derivative of t-butyl amine

A polyoxyalkyleneamine containing both ethylene oxide and propyleneoxide units derived from a t-butyl amine has the following structure:

Such a compound is prepared by reacting 15 moles of ethylene oxide and 5moles of propylene oxide with t-butyl amine to form polyetherdiol. Thepolyetherdiol is then reductively aminated with ammonia and hydrogen toprovide polyethers with terminal aminic groups, wherein the primaryaliphatic amine content is 1.674 meq N/g.

Example A

125 grams of PolyPIBSA 1000, as prepared in Example 2, were charged intoa 500 mL stirred glass reactor. A constant 180 mL/min nitrogen purgethrough the reactor headspace was then started. The reactor was heatedto 160° C. When the reactor temperature attained 160° C., 8.53 grams ofN-phenyl-1,4-phenylenediamine, 13.32 grams of an ethylene oxide andpropylene oxide based polyoxyalkyleneamine withN-phenyl-1,4-phenylenediamine core—wherein the primary aliphatic aminecontent is 1.91 meq N/g, prepared as in Example 5, 13.9 grams of anethylene oxide and propylene oxide based polyoxyalkyleneamine with atert-butylamine core, as prepared in Example 6, and 38.58 grams ofdiluent oil were added to the reactor sequentially. The reaction mixturewas held at 160° C. for 1.5 hours. The reactor pressure was then reducedto <20 mmHg (abs) to remove any water generated during the reaction. Thevacuum conditions were maintained for 30 minutes. The reactiontemperature was maintained for another 16.5 hours because the reactionappeared to be incomplete.

The reactor pressure was again reduced to <20 mmHg (abs) and maintainedfor 30 minutes to remove any water generated during the reaction.

Examples A and B in Table 1 are examples of the method of preparing theinvention. Example B was generated using the conditions of Example Aexcept various reagents and concentrations of those reagents weresubstituted for those listed in Example A (see Table 1).

Example C

323.44 grams (0.0694 moles anhydride) of PIBSA 2300 (saponificationnumber=35.5 mg KOH/g), as prepared in Example 4, and 26.10 grams of analpha olefin/maleic anhydride copolymer (saponification number=94.0 mgKOH/g; alpha olefin average molecular weight ˜168 g/mol), as prepared inExample 3, were charged into a 500 mL stirred glass reactor. A constant150 mL/min nitrogen purge through the reactor headspace was thenstarted. The reactor, was heated to approximately 160° C. When thereactor temperature approached 160° C., 28.73 grams of an ethylene oxideand propylene oxide based polyoxyalkyleneamine with a tert-butylaminecore, as prepared in Example 6, and 25.18 grams of an ethylene oxide andpropylene oxide based polyoxyalkyleneamine withN-phenyl-1,4-phenylenediamine core—wherein the primary aliphatic aminecontent is 1.91 meq N/g, prepared as in Example 5 were added to thereactor. The reaction mixture was held at 160° C. for about 1.5 hours.The reactor pressure was then reduced to <20 mmHg (abs) to remove anywater, generated during the reaction. The vacuum conditions weremaintained for about 30 minutes.

Examples C and D in Table 1 are examples of the method of preparing theinvention. Example D was generated using the conditions of Example Cexcept various reagents and concentrations of those reagents weresubstituted for those listed in Example C (see Table 1).

Ex. 4 Aromatic Aliphatic Dilcent Copolymer PIBSA Polyether AromaticCompound Aliphatic Compound Oil Example Copolymer (g) (g) Polyether (g)Compound (g) Compound (g) (g) A Example 2 125 0 Ex. 6/Ex. 5  13.9/13.32NPPDA 8.53 None 0 38.58 B Example 1 150 0 Ex. 6/Ex. 5 12.05/11.55 NPPDA3.7 None 0 18.72 C Example 3 26.10 323.44 Ex. 6/Ex. 5 28.73/25.18 NPPDA8.95 None 0 0 D Example 3 27.43 339.92 Ex. 6/Ex. 5 45.75/40.10 None 0None 0 0 E Example 3 47.62 296.6 Ex. 6/Ex. 5 26.75/23.44 NPPDA 8.13 None0 0 F Example 3 51.36 319.89 Ex. 6/Ex. 5 43.06/37.74 None 0 None 0 0NPPDA: N-phenyl-1,4-phenylenediamine

Examples A-F, which exemplify the lubricating oil additive compositionof the present invention, were evaluated for percent viscosity increaseusing a soot thickening bench test, which measures the ability of theformulation to disperse and control viscosity increase, resulting fromthe addition of carbon black, a soot surrogate. Using the sootthickening bench test, the viscosity of a fresh oil is measured incentistokes. The fresh oil is then treated with 2 wt % Vulcan XC 72Rcarbon black, supplied by Columbia Chemical Co., to form a mixturecontaining approximately 2 grams Vulcan XC72R carbon black and 98 gramsfresh oil (test oil). The test oil, which contains carbon black, is thenleft to sit overnight. It is then homogenized using a high speed tissuehomogenizer for approximately 60 seconds to thoroughly mix the carbonblack with the fresh oil. The resulting test oil containing carbon blackis then degassed at 100° C. for 30 minutes. The viscosity of the oilcontaining carbon black is measured according to methods that are wellknown in the art. The percent viscosity increase is calculated accordingto the following formula:% viscosity increase=[(vis_(cbo)−vis_(fo))/(vis_(fo))×100]

-   -   vis_(cbo): viscosity of carbon black in oil    -   vis_(fo): viscosity of fresh oil

Using the soot thickening bench test, the percent viscosity increasecalculated for the additive composition of Examples A-F in a formulatedoil was compared to a formulated oil that does not contain thelubricating oil additive composition of the present invention. Theformulated oil of the present invention comprises 0.66 wt % of anoxidation inhibitor package, 0.33 wt & pour point depressant, 4.07 wt %of a calcium based detergent package containing a phenate andsulfonates, 2.41 wt % zinc dithiophosphate, 0.03 wt % foam inhibitor,7.7 wt % viscosity index improver and 85.10 wt % of a lube oil blendwhich is a mixture of basestocks that consists of 69.24 wt % Exxon150Noil, and 30.76 wt % Exxon600N oil (all of which may be purchased fromExxonMobil Corporation, Fairfax, Va.) to provide the comparative oilformulation. To prepare the formulated lubricating oil composition ofthe present invention, approximately 7.6 wt % of the additivecomposition of Examples A-F were top treated to the formulatedcomparison oil.

The results, of the soot thickening bench test are summarized in Table2.

TABLE 2 Soot Thickening Bench Test Results Example % Viscosity increaseA 30.39 B 32.11 C 27.24 D 28.81 E 26.55 F 24.87 No 283.9 Dispersant

The results of the soot thickening bench test indicate that the percentviscosity increase using the lubricating oil additive composition of thepresent invention was lower than the percent viscosity increase in aformulated oil that did not contain a lubricating oil additivecomposition of the present invention, which yielded approximately a 284%viscosity increase. This test indicates that the lubricating oiladditive composition of the present invention has good dispersantproperties.

It is understood that although modifications and variations of theinvention can be made without departing from the spirit and scopethereof, only such limitations should be imposed as are indicated in theappended claims.

1. An oil-soluble lubricating oil additive composition prepared by the process which comprises reacting (A) at least one of the following copolymers: a copolymer obtained by free radical copolymerization of components comprising: (a) at least one monoethylenically unsaturated C₃-C₂₈ monocarboxylic acid or ester thereof, or C₄-C₂₈ dicarboxylic acid, anhydride or ester thereof; (b) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one polyolefin comprising about 4 to 360 carbon atoms and having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof; and (c) at least one monoolefin compound which is copolymerizable with the monomers of (a) and (b) and is selected from the group consisting of: (1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl group is hydroxyl, amino, dialkylamino or alkoxy substituted or is unsubstituted, and containing from about 1 to about 40 carbon atoms; (2) an alkyl amine and an N-alkylamide of a monoethylenically unsaturated mono- or dicarboxylic acid of from about 3 to about 10 carbon atoms where the alkyl substituent contains from about 1 to about 40 carbon atoms; (3) an N-vinylcarboxamide of carboxylic acids of from about 1 to about 8 carbon atoms; (4) an N-vinyl substituted nitrogen-containing heterocyclic compound; and (5) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one polyolefin comprising about 4 to about 360 carbon atoms and having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof, provided that the olefin employed is not the same as the olefin employed in (i)(b); (ii) a copolymer obtained by reacting compound (i)(a) and compound (i)(b) in the presence of a free radical initiator; or (iii) a copolymer obtained by (a) reacting compound (i)(a) with compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in the presence of copolymer (i) or copolymer (ii) or both; or by (b) contacting copolymer (i) or copolymer (ii) or both with the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c); with (B) at least one polyether aromatic compound capable of being reacted with at least two monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids, anhydrides or esters thereof, or mixtures thereof; and (C) at least one polyether aliphatic amine compound capable of being reacted with at least two monocarboxylic acids or esters thereof; or at least two dicarboxylic acids, anhydrides, or esters thereof or mixtures thereof.
 2. The lubricating oil additive composition of claim 1, wherein copolymer (i), (ii) or (iii) is reacted with at least one polyether aromatic compound, with at least one polyether aliphatic compound and, additionally, with (1) at least one ether compound; (2) at least one aromatic compound capable of being reacted with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof; or (3) at least one aliphatic compound capable of being reacted with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof or mixtures of (1), (2) or (3).
 3. The lubricating oil additive composition of claim 2, wherein in copolymer (iii)(b), said copolymer (i) or copolymer (ii) or both are contacted with the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c) in the presence of component (2), component (3) or mixtures thereof.
 4. The lubricating additive composition of claim 1, wherein the polyether aromatic compound is derived from an aromatic amine having the following formula (a) an N-arylphenylenediamine represented by the formula:

R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl, —CH₂-aryl-NH₂, in which n and m each have a value from about 1 to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms, (b) aminocarbazole represented by the formula:

in which R₂₁ and R₂₂ each independently represent hydrogen or an alkyl or alkenyl radical having from about 1 to about 14 carbon atoms, (c) an amino-indazolinone represented by the formula:

in which R₂₃ is hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; and (d) an aminomercaptotriazole represented by the formula:

(e) an aminoperimidine represented by the formula:

in which R₂₄ represents hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; (f) an aryloxyphenyleneamine represented by the formula:

in which R₂₅ is H, —NHaryl, —NHalkaryl, or branched or straight chain radical having from about 4 to about 24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₂₆ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, or —NHaralkyl, in which n and m each have a value from about 1 to about 10; and R₂₇ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms; provided that when R₂₅ is hydrogen or a branched or straight chain radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl, then R₂₆ must be NH₂ or —(NH(CH₂)_(n))_(m)NH₂, —CH₂—(CH₂)_(n)—NH₂, or —CH₂-aryl-NH₂, (g) an aromatic amine comprising two aromatic groups, linked by a group, L, represented by the following formula:

wherein L is selected from —O—, —N═N—, —NH—, —CH₂NH, —C(O)NR₂₈—, —C(O)O—, —SO₂—, —SO₂NR₂₉— or —SO₂NH—, wherein R₂₈ and R₂₉ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms; wherein each Y₁, Y₂, Y₃ and Y₄ are independently N or CH provided that Y₁ and Y₂ may not both be N; R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂, —SO₃H, —SO₃Na, CO₂H or salt thereof, —NR₄₁R₄₂ wherein R₄₁ and R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or alkaryl; R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms, —OH, —SO₃H or —SO₃Na; R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10; provided that when R₃₄ is —NHR₃₅ wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, then either L is —NH— or —CH₂—NH—; or R₃₀ or R₃₁ is OH or —NR₄₁R₄₂ wherein at least one of R₄₁ or R₄₂ is hydrogen; or R₃₂ or R₃₃ is OH, (h) an aminothiazole selected from the group consisting of aminothiazole, aminobenzothiazole, aminobenzothiadiazole and aminoalkylthiazole; (i) an aminoindole represented by the formula:

wherein R₃₆ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (j) an aminopyrrole represented by the formula:

wherein R₃₇ represents a divalent alkylene group having about 2 to about 6 carbon atoms and R₃₈ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (k) a ring substituted or unsubstituted aniline, such as nitroaniline or 4-aminoacetanilide; (l) an aminoquinoline; (m) an aminobenzimidazole; (n) a N,N-dialkylphenylenediamine; and (o) a benzylamine.
 5. The lubricating oil additive composition of claim 4, wherein the polyether aromatic compound is derived from an aromatic amine having the following formula

R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl, —CH₂-aryl-NH₂, in which n and m each have a value from about 1 to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms.
 6. The lubricating oil additive composition of claim 4 wherein the polyether aromatic compound is derived from the following formula:

wherein L is selected from —O—, —N═N—, —NH—, or —CH₂NH; R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂ or, —NR₄₁R₄₂ wherein R₄₁ and R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or alkaryl; R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms, or —OH; R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10; provided that when R₃₄ is —NHR₃₅ wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, then either L is —NH— or —CH₂—NH—; or R₃₀ or R₃₁ is OH or —NR₄₁R₄₂ wherein at least one of R₄₁ or R₄₂ is hydrogen; or R₃₂ or R₃₃ is OH.
 7. The lubricating oil additive composition of claim 4 wherein the polyether aromatic compound is derived from N-phenyl-1,4-phenylenediamine.
 8. The lubricating oil additive composition of claim 4 wherein the polyether aromatic compound is derived from 4-(4-nitrophenylazo) aniline or 4-phenylazoaniline.
 9. The lubricating oil additive composition of claim 6, wherein the polyether aromatic compound is derived from 4-phenoxyaniline.
 10. The lubricating oil additive composition of claim 1, wherein the polyether aliphatic amine compound is derived from an aliphatic amino hydroxyl compound.
 11. The lubricating oil additive composition of claim 1 wherein the polyether aliphatic amine compound is derived from t-butyl amine dimethylaminopropylamine, N-aminopropylmorpholine, diethylaminopropylamine, or diethylaminoethylamine.
 12. The lubricating oil additive composition of claim 11, wherein the polyether aliphatic amine is derived from t-butyl amine.
 13. The lubricating oil additive composition of claim 1 wherein the copolymer is copolymer (i).
 14. The lubricating oil additive composition of claim 1 wherein the copolymer is copolymer (ii).
 15. The lubricating oil additive composition of claim 14 wherein copolymer (ii) is polyPIBSA, obtained by the free radical catalyzed reaction of maleic anhydride and polyisobutylene.
 16. The lubricating oil additive composition of claim 1 wherein the copolymer is copolymer (iii).
 17. The lubricating oil additive composition of claim 2 wherein the aromatic compound is selected from the group consisting of: (a) an N-arylphenylenediamine represented by the formula:

R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R(2)₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl, —CH₂-aryl-NH₂, in which n and m each have a value from about 1 to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms, (b) aminocarbazole represented by the formula:

in which R₂₁ and R₂₂ each independently represent hydrogen or an alkyl or alkenyl radical having from about 1 to about 14 carbon atoms, (c) an amino-indazolinone represented by the formula:

in which R₂₃ is hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; and (d) an aminomercaptotriazole represented by the formula:

(e) an aminoperimidine represented by the formula:

in which R₂₄ represents hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; (f) an aryloxyphenyleneamine represented by the formula:

in which R₂₅ is H, —NHaryl, —NHalkaryl, or branched or straight chain radical having from about 4 to about 24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₂₆ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, or —NHaralkyl, in which n and m each have a value from about 1 to about 10; and R₂₇ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms; (g) an aromatic amine comprising two aromatic groups, linked by a group, L, represented by the following formula:

wherein L is selected from —O—, —N═N—, —NH—, —CH₂NH, —C(O)NR₂₈—, —C(O)O—, —SO₂—, —SO₂NR₂₉— or —SO₂NH—, wherein R₂₈ and R₂₉ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms; wherein each Y₁, Y₂, Y₃ and Y₄ are independently N or CH provided that Y₁ and Y₂ may not both be N; R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂, —SO₃H, —SO₃Na, CO₂H or salt thereof, —NR₄₁R₄₂ wherein R₄₁ and R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or alkaryl; R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms, —OH, —SO₃H or —SO₃Na; R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10; (h) an aminothiazole selected from the group consisting of aminothiazole, aminobenzothiazole, aminobenzothiadiazole and aminoalkylthiazole; (i) an aminoindole represented by the formula:

wherein R₃₆ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (j) an aminopyrrole represented by the formula:

wherein R₃₇ represents a divalent alkylene group having about 2 to about 6 carbon atoms and R₃₈ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (k) a ring substituted or unsubstituted aniline, such as nitroaniline or 4-aminoacetanilide; (l) an aminoquinoline; (m) an aminobenzimidazole; (n) a N,N-dialkylphenylenediamine; (o) a benzylamine; and (p) a benzyl alcohol.
 18. The lubricating oil additive composition of claim 17 wherein the aromatic amine is N-arylphenylenediamine.
 19. The lubricating oil additive composition of claim 18 wherein the N-arylphenylenediamine is N-phenylphenylenediamine.
 20. The lubricating oil additive composition of claim 19 wherein the N-phenylphenylenediamine is N-phenyl-1,4-phenylenediamine.
 21. The lubricating oil additive composition of claim 1 wherein compound (i)(b) of copolymer (i) is polyisobutene having a number average molecular weight (Mn) of from about 112 to about
 5000. 22. The lubricating oil additive composition of claim 21 wherein the number average molecular weight (Mn) is from about 500 to about
 3000. 23. The lubricating oil additive composition of claim 22 wherein the number average molecular weight (Mn) is from about 1000 to about
 2500. 24. The lubricating oil additive composition of claim 1 wherein (i)(a) is a dicarboxylic acid, anhydride or ester thereof.
 25. The lubricating oil additive composition of claim 24 wherein (i) (a) is maleic anhydride or ester thereof.
 26. The lubricating oil additive composition of claim 1 wherein the monoolefin of (i)(c) is a 1-olefin.
 27. A lubricating oil composition comprising a major amount of an oil of lubricating viscosity and a minor amount of the lubricating oil additive composition prepared by the process which comprises reacting (A) at least one of the following copolymers: (i) a copolymer obtained by free radical copolymerization of components comprising: (a) at least one monoethylenically unsaturated C₃-C₂₈ monocarboxylic acid or ester thereof, or a C₄-C₂₈ dicarboxylic acid, anhydride or ester thereof; (b) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one polyolefin comprising about 4 to 360 carbon atoms and having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof; and (c) at least one monoolefin compound which is copolymerizable with the monomers of (a) and (b) and is selected from the group consisting of: (1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl group is hydroxyl, amino, dialkylamino or alkoxy substituted or is unsubstituted, and containing from about 1 to about 40 carbon atoms; (2) an alkyl amine and an N-alkylamide of a monoethylenically unsaturated mono- or dicarboxylic acid of from about 3 to about 10 carbon atoms where the alkyl substituent contains 1 to 40 carbon atoms; (3) an N-vinylcarboxamide of carboxylic acids of from about 1 to about 8 carbon atoms; (4) an N-vinyl substituted nitrogen-containing heterocyclic compound; and (5) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one polyolefin comprising about 4 to about 360 carbon atoms and having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof, provided that the olefin employed is not the same as the olefin employed in (i)(b); (ii) a copolymer obtained by reacting compound (i)(a) and compound (i)(b) in the presence of a free radical initiator; or (iii) a copolymer obtained by (a) reacting compound (i)(a) with compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in the presence of copolymer (i) or copolymer (ii) or both; or by (b) contacting copolymer (i) or copolymer (ii) or both with the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c); with (B) at least one polyether aromatic compound capable of being reacted with at least two monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids, anhydrides or esters thereof, or mixtures thereof; and (C) at least one polyether aliphatic amine compound capable of being reacted with at least two monocarboxylic acids or esters thereof; or at least two dicarboxylic acids, anhydrides, or esters thereof; or mixtures thereof.
 28. The lubricating oil composition of claim 27, wherein copolymer (i), (ii) or (iii) is reacted with at least one polyether aromatic compound and additionally with (1) at least one aromatic compound capable of being reacted with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof, or (2) at least one aliphatic compound capable of being reacted with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof, or mixtures of (1) or (2) or both.
 29. The lubricating oil composition of claim 28, wherein in copolymer (iii)(b), said copolymer (i) or copolymer (ii) or both are contacted with the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c) in the presence of component (1), component (2) or both.
 30. The lubricating composition of claim 27, wherein the polyether aromatic compound is derived from an aromatic amine having the following formula (a) an N-arylphenylenediamine represented by the formula:

R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl, —CH₂-aryl-NH₂, in which n and m each have a value from about 1 to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms, (b) aminocarbazole represented by the formula:

in which R₂₁ and R₂₂ each independently represent hydrogen or an alkyl or alkenyl radical having from about 1 to about 14 carbon atoms, (c) an amino-indazolinone represented by the formula:

in which R₂₃ is hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; and (d) an aminomercaptotriazole represented by the formula:

(e) an aminoperimidine represented by the formula:

in which R₂₄ represents hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; (f) an aryloxyphenyleneamine represented by the formula:

in which R₂₅ is H, —NHaryl, —NHalkaryl, or branched or straight chain radical having from about 4 to about 24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₂₆ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, or —NHaralkyl, in which n and m each have a value from about 1 to about 10; and R₂₇ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms; provided that when R₂₅ is hydrogen or a branched or straight chain radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl, then R₂₆ must be NH₂ or —(NH(CH₂)_(n))_(m)NH₂, —CH₂—(CH₂)_(n)—NH₂, or —CH₂-aryl-NH₂, (g) an aromatic amine comprising two aromatic groups, linked by a group, L, represented by the following formula:

wherein L is selected from —O—, —N═N—, —NH—, —CH₂NH, —C(O)NR₂₈—, —C(O)O—, —SO₂—, —SO₂NR₂₉— or —SO₂NH—, wherein R₂₈ and R₂₉ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms; wherein each Y₁, Y₂, Y₃ and Y₄ are independently N or CH provided that Y₁ and Y₂ may not both be N; R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂, —SO₃H, —SO₃Na, CO₂H or salt thereof, —NR₄₁R₄₂ wherein R₄₁ and R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or alkaryl; R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms, —OH, —SO₃H or —SO₃Na; R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10; provided that when R₃₄ is —NHR₃₅ wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, then either L is —NH— or —CH₂—NH—; or R₃₀ or R₃₁ is OH or —NR₄₁R₄₂ wherein at least one of R₄₁ or R₄₂ is hydrogen; or R₃₂ or R₃₃ is OH, (h) an aminothiazole selected from the group consisting of aminothiazole, aminobenzothiazole, aminobenzothiadiazole and aminoalkylthiazole; (i) an aminoindole represented by the formula:

wherein R₃₆ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (j) an aminopyrrole represented by the formula:

wherein R₃₇ represents a divalent alkylene group having about 2 to about 6 carbon atoms and R₃₈ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (k) a ring substituted or unsubstituted aniline, such as nitroaniline or 4-aminoacetanilide; (l) an aminoquinoline; (m) an aminobenzimidazole; (n) a N,N-dialkylphenylenediamine; and (o) a benzylamine.
 31. The lubricating oil composition of claim 30, wherein the polyether aromatic compound is derived from an aromatic amine having the following formula

R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl, —CH₂-aryl-NH₂, in which n and m each have a value from about 1 to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms.
 32. The lubricating oil composition of claim 30 wherein the polyether aromatic compound is derived from the following formula:

wherein L is selected from —O—, —N═N—, —NH—, or —CH₂NH; R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, or, —NR₄₁R₄₂ wherein R₄₁ and R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or alkaryl; R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms, or —OH; R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10; provided that when R₃₄ is —NHR₃₅ wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, then either L is —NH— or —CH₂—NH—; or R₃₀ or R₃₁ is OH or —NR₄₁R₄₂ wherein at least one of R₄₁ or R₄₂ is hydrogen; or R₃₂ or R₃₃ is OH.
 33. The lubricating oil composition of claim 31 wherein the polyether aromatic compound is derived from N-phenyl-1,4-phenylenediamine.
 34. The lubricating oil composition of claim 27, wherein the polyether aromatic compound is derived from 4-(4-nitrophenylazo)aniline, 4-phenylazoaniline.
 35. The lubricating oil composition of claim 27, wherein the polyether aromatic compound is derived from 4-phenoxyaniline.
 36. The lubricating oil composition of claim 27, wherein the polyether aliphatic amine compound is derived from an aliphatic amino hydroxyl compound.
 37. The lubricating oil composition of claim 27 wherein the polyether aliphatic amine compound is derived from t-butyl amine dimethylaminopropylamine, N-aminopropylmorpholine, diethylaminopropylamine, or diethylaminoethylamine.
 38. The lubricating oil composition of claim 37, wherein the polyether aliphatic amine is derived from t-butyl amine.
 39. The lubricating oil composition of claim 27 wherein the copolymer is copolymer (i).
 40. The lubricating oil composition of claim 27 wherein the copolymer is copolymer (ii).
 41. The lubricating oil composition of claim 40 wherein copolymer (ii) is polyPIBSA, obtained by the free radical catalyzed reaction of maleic anhydride and polyisobutylene.
 42. The lubricating oil composition of claim 27 wherein the copolymer is copolymer (iii).
 43. The lubricating oil composition of claim 28 wherein the aromatic compound is selected from the group consisting of: (a) an N-arylphenylenediamine represented by the formula:

R₁₈ is H, —NHaryl, —NHalkaryl, or a branched or straight chain hydrocarbyl radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R(2)₁₉ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, —NHaralkyl, —CH₂-aryl-NH₂, in which n and m each have a value from about 1 to about 10; and R₂₀ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms, (b) aminocarbazole represented by the formula:

in which R₂₁ and R₂₂ each independently represent hydrogen or an alkyl or alkenyl radical having from about 1 to about 14 carbon atoms, (c) an amino-indazolinone represented by the formula:

in which R₂₃ is hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; and (d) an aminomercaptotriazole represented by the formula:

(e) an aminoperimidine represented by the formula:

in which R₂₄ represents hydrogen or an alkyl radical having from about 1 to about 14 carbon atoms; (g) an aryloxyphenyleneamine represented by the formula:

in which R₂₅ is H, —NHaryl, —NHalkaryl, or branched or straight chain radical having from about 4 to about 24 carbon atoms that can be alkyl, alkenyl, alkoxyl, aralkyl or alkaryl; R₂₆ is —NH₂, —(NH(CH₂)_(n))_(m)NH₂, —NHalkyl, or —NHaralkyl, in which n and m each have a value from about 1 to about 10; and R₂₇ is hydrogen, alkyl, alkenyl, alkoxyl, aralkyl, or alkaryl, having from about 4 to about 24 carbon atoms; provided that when R₂₅ is hydrogen or a branched or straight chain radical having from about 4 to about 24 carbon atoms selected from alkyl, alkenyl, alkoxyl, aralkyl or alkaryl, then R₂₆ must be NH₂ or —(NH(CH₂)_(n))_(m)NH₂, —CH₂—(CH₂)_(n)—NH₂, or —CH₂-aryl-NH₂, (h) an aromatic amine comprising two aromatic groups, linked by a group, L, represented by the following formula:

wherein L is selected from —O—, —N═N—, —NH—, —CH₂NH, —C(O)NR₂₈—, —C(O)O—, —SO₂—, —SO₂NR₂₉— or —SO₂NH—, wherein R₂₈ and R₂₉ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms; wherein each Y₁, Y₂, Y₃ and Y₄ are independently N or CH provided that Y₁ and Y₂ may not both be N; R₃₀ and R₃₁ independently represent a hydrogen, alkyl, aryl, alkaryl, aralkyl, alkoxy, hydroxyalkyl, aminoalkyl, —OH, —NO₂, —SO₃Na, CO₂H or salt thereof, —NR₄₁R₄₂ wherein R₄₁ and R₄₂ are independently hydrogen, alkyl, aryl, arylalkyl, or alkaryl; R₃₂ and R₃₃ independently represent a hydrogen, an alkyl, an alkenyl or an alkoxy group having from about 1 to about 8 carbon atoms, —OH, —SO₃H or —SO₃Na; R₃₄ represents —NH₂, —NHR₃₅, wherein R₃₅ is an alkyl or an alkenyl group having from about 1 to about 8 carbon atoms, —CH₂—(CH₂)_(n)—NH₂ or —CH₂-aryl-NH₂ and n is from 0 to about 10; (h) an aminothiazole selected from the group consisting of aminothiazole, aminobenzothiazole, aminobenzothiadiazole and aminoalkylthiazole; (i) an aminoindole represented by the formula:

wherein R₃₆ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (j) an aminopyrrole represented by the formula:

wherein R₃₇ represents a divalent alkylene group having about 2 to about 6 carbon atoms and R₃₈ represents a hydrogen, an alkyl or an alkenyl group having from about 1 to about 14 carbon atoms; (k) a ring substituted or unsubstituted aniline, such as nitroaniline or 4-aminoacetanilide; (l) an aminoquinoline; (m) an aminobenzimidazole; (n) a N,N-dialkylphenylenediamine; (o) a benzylamine; and (p) a benzyl alcohol.
 44. The lubricating oil composition of claim 43 wherein the aromatic amine is N-arylphenylenediamine.
 45. The lubricating oil composition of claim 44 wherein the N-arylphenylenediamine is N-phenylphenylenediamine.
 46. The lubricating oil composition of claim 45 wherein the N-phenylphenylenediamine is N-phenyl-1,4-phenylenediamine.
 47. The lubricating oil composition of claim 27 wherein compound (i)(b) of copolymer (i) is polyisobutene having a number average molecular weight (Mn) of from about 112 to about
 5000. 48. The lubricating oil composition of claim 47 wherein the number average molecular weight (Mn) is from about 500 to about
 3000. 49. The lubricating oil composition of claim 48 wherein the number average molecular weight (Mn) is from about 1000 to about
 2500. 50. The lubricating oil composition of claim 27 wherein (i)(a) is a dicarboxylic acid, anhydride or ester thereof.
 51. The lubricating oil composition of claim 50 wherein (i)(a) is maleic anhydride or ester thereof.
 52. The lubricating oil additive composition of claim 27 wherein the monoolefin of (i)(c) is a 1-olefin.
 53. A method of making a lubricating oil additive composition which comprises reacting (A) at least one of the following copolymers: (i) a copolymer obtained by free radical copolymerization of components comprising: (a) at least one monoethylenically unsaturated C₃-C₂₈ monocarboxylic acid or ester thereof, or a C₄-C₂₈ dicarboxylic acid, anhydride or ester thereof; (b) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one polyolefin comprising about 4 to 360 carbon atoms and having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof; and (c) at least one monoolefin compound which is copolymerizable with the monomers of (a) and (b) and is selected from the group consisting of: (1) an alkyl vinyl ether and an allyl alkyl ether where the alkyl group is hydroxyl, amino, dialkylamino or alkoxy substituted or is unsubstituted, and containing from about 1 to about 40 carbon atoms; (2) an alkyl amine and an N-alkylamide of a monoethylenically unsaturated mono- or dicarboxylic acid of from about 3 to about 10 carbon atoms where the alkyl substituent contains from about 1 to about 40 carbon atoms; (3) an N-vinylcarboxamide of carboxylic acids of from about 1 to about 8 carbon atoms; (4) an N-vinyl substituted nitrogen-containing heterocyclic compound; and (5) at least one 1-olefin comprising about 2 to 40 carbon atoms or at least one polyolefin comprising about 4 to about 360 carbon atoms and having a terminal copolymerizable group in the form of a vinyl, vinylidene or alkyl vinylidene group or mixtures thereof, provided that the olefin employed is not the same as the olefin employed in (i)(b); (ii) a copolymer obtained by reacting compound (i)(a) and compound (i)(b) in the presence of a free radical initiator; (iii) a copolymer obtained by (a) reacting compound (i)(a) with compound (i)(b) or (i)(c) in a non-free radical catalyzed reaction in the presence of copolymer (i) or copolymer (ii) or both; or by (b) contacting copolymer (i) or copolymer (ii) or both with the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c); with (B) at least one polyether aromatic compound capable of being reacted with at least two monocarboxylic acids or esters thereof, or with at least two dicarboxylic acids, anhydrides or esters thereof, or mixtures thereof; and (C) at least one polyether aliphatic amine compound capable of being reacted with at least two monocarboxylic acids or esters thereof; or at least two dicarboxylic acids, anhydrides, or esters thereof; or mixtures thereof.
 54. The method of making the lubricating oil additive composition of claim 53, wherein copolymer (i), (ii) or (iii) is reacted with at least one polyether aromatic compound and additionally with (1) at least one aromatic compound capable of being reacted with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof, or (2) at least one aliphatic compound capable of being reacted with at least one monocarboxylic acid or ester thereof, or dicarboxylic acid, anhydride or ester thereof, or mixtures of (1) or (2) or both.
 55. The method of making the lubricating oil additive composition of claim 54, wherein in copolymer (iii)(b), said copolymer (i) or copolymer (ii) or both are contacted with the non-free radical catalyzed reaction product of compound (i)(a) and compound (i)(b) or (i)(c) in the presence of component (1), component (2) or both.
 56. A method of improving soot dispersancy, sludge dispersancy or both in an internal combustion engine which comprises operating the engine with the lubricating oil composition comprising a major amount of oil of lubricating viscosity and an effective amount of the lubricating oil additive composition of claim
 1. 57. The lubricating oil additive composition of claim 4 wherein the aromatic amine is 4-benzoylamine-2,5-dimethoxyaniline or N-(4-aminophenyl)acetamide.
 58. The lubricating oil additive composition of claim 4 wherein the aromatic amine 3-nitroaniline.
 59. The lubricating oil additive composition of claim 17 wherein the aromatic compound is phenoxyaniline, 4-(4-nitrophenylazo)aniline or 4-phenylazoaniline.
 60. The lubricating oil additive composition of claim 17 wherein the aromatic compound is 4-benzoylamine-2,5-dimethoxyaniline or N-(4-aminophenyl)acetamide.
 61. The lubricating oil additive composition of claim 17 wherein the aromatic compound is 3-nitroaniline.
 62. The lubricating oil additive composition of claim 5 wherein the aromatic amine is N-phenyl-1,4-phenylenediamine.
 63. The lubricating oil additive composition of claim 6 wherein aromatic amine is 4-(4-nitrophenylazo)aniline or 4-phenylazoaniline.
 64. The lubricating oil additive composition of claim 6 wherein the aromatic amine is 4-phenoxyaniline. 